Acrylonitrile compounds, process for their production and pesticides containing them

ABSTRACT

Acrylonitrile compounds having pesticidal activity of formula (I) and salts thereof.                    
     wherein Q is                    
     Y is ═C(R 4 )— or ═N—, R 1  is alkyl, haloalkyl, etc., each of R 2  and R 3  is halogen, alkyl which may be substituted, alkenyl which may be substituted, etc., R 4  is hydrogen, halogen, alkyl or haloalkyl, 1 is from 1 to 4, m is from 0 to 5, n is from 0 to 3, q is from 0 to 4, when 1 is 2 or more, a plurality of R 2  may be the same or different, when each of m, n and q is 2 or more, a plurality of R 3  may be the same or different.

This application is a 371 of PCT/JP98/00584 filed Feb. 13, 1998.

DESCRIPTION

The present invention relates to novel acrylonitrile compounds useful asactive ingredients for pesticides.

(1) EP 104690A, EP 62238A and U.S. Pat. No. 4,469,688, respectively,disclose compounds similar to the compounds of the present invention,but such compounds and the compounds of the present invention aredifferent in their chemical structures.

(2) EP 776879A discloses a process for producing an enol ether whichliterally covers a part of the compounds of the present invention, butin this publication, there is no specific disclosure at all with respectto the group of compounds of the present invention.

(3) JP-A-60-11401 and JP-A-60-11452, respectively, discloseα-cyanoketone derivatives which literally cover a part of the compoundsof the present invention, but in these publications, there is nospecific disclosure at all with respect to the group of compounds of thepresent invention.

(4) U.S. Pat. No. 3,337,565 discloses acrylonitrile derivatives whichliterally cover a part of the compounds of the present invention, but inthis publication, there is no specific disclosure at all with respect tothe group of compounds of the present invention.

(5) U.S. Pat. No. 3,337,566 discloses acrylonitrile derivatives similarto the compounds of the present invention, but such derivatives and thecompounds of the present invention are different in their chemicalstructures.

(6) WO97/40009 discloses ethylene derivatives similar to the compoundsof the present invention, but the derivatives and the compounds of thepresent invention are different in their chemical structures.

(7) Bulletin de la Societe Chimique de France, 1980, No. 3-4, p.163-166, discloses 3-(4-chlorophenyl)-2-phenyl-3-ethoxyacrylonitrile,but this compound and the compounds of the present invention aredifferent in their chemical structures.

(8) Journal of Chemical Research (Synopses), 1987, p. 78-79, discloses2-(3,5-dimethoxyphenyl)-3-(2-methoxy-4-methylphenyl)-3-acetoxyacrylonitrileand2-(3,5-dimethoxyphenyl)-3-(2,6-dimethoxy-4-methylphenyl)-3-acetoxyacrylonitrile,but these compounds and the compounds of the present invention aredifferent in their chemical structures.

The present inventors have conducted various studies to find out anexcellent pesticide, paying an attention to acrylonitrile compounds and,as a result, have accomplished the present invention.

Namely, the present invention provides an acrylonitrile compound of thefollowing formula (I) or its salt:

wherein Q is

Y is ═C(R₄)— or ═N—, R₁ is alkyl, haloalkyl, alkoxyalkyl,alkylthioalkyl, alkenyl, haloalkenyl, alkynyl, haloalkynyl, —C(═O)R₅,—C(═S)R₅, —S(O)_(w)R₅ or —CH₂R₉, each of R₂ and R₃ is halogen, alkylwhich may be substituted, alkenyl which may be substituted, alkynylwhich may be substituted, alkoxy which may be substituted, alkenyloxywhich may be substituted, alkynyloxy which may be substituted, alkylthiowhich may be substituted, alkylsulfinyl which may be substituted,alkylsulfonyl which may be substituted, alkenylthio which may besubstituted, alkenylsulfinyl which may be substituted, alkenylsulfonylwhich may be substituted, alkynylthio which may be substituted,alkynylsulfinyl which may be substituted, alkynylsulfonyl which may besubstituted, nitro, cyano, phenyl which may be substituted, phenoxywhich may be substituted, phenylthio which may be substituted,phenylsulfinyl which may be substituted, phenylsulfonyl which may besubstituted, benzyl which may be substituted, benzyloxy which may besubstituted, benzylthio which may be substituted, or benzoyl which maybe substituted, R₄ is hydrogen, halogen, alkyl or haloalkyl, R₅ is alkylwhich may be substituted, alkenyl which may be substituted, alkynylwhich may be substituted, alkoxy which may be substituted, alkenyloxywhich may be substituted, alkynyloxy which may be substituted, alkylthiowhich may be substituted, alkenylthio which may be substituted,alkynylthio which may be substituted, cycloalkyl, cycloalkyloxy,cycloalkylthio, —N(R₇)R₈, phenyl which may be substituted, phenoxy whichmay be substituted, phenylthio which may be substituted, benzyl whichmay be substituted, benzyloxy which may be substituted, benzylthio whichmay be substituted, —J, —O—J or —S—J, each of R₇ and R₈ is hydrogen,alkyl or alkoxy, R₉ is cyano, phenyl which may be substituted, phenoxywhich may be substituted, phenylthio which may be substituted,phenylsulfinyl which may be substituted, phenylsulfonyl which may besubstituted, benzyl which may be substituted, benzyloxy which may besubstituted, benzylthio which may be substituted, benzoyl which may besubstituted, —J, —C(═O)R₁₀, —C(═S)R₁₀, —S(O)_(w)R₁₀ or trimethylsilyl,R₁₀ is alkyl or alkoxy, J is a 5- or 6-membered heterocyclic groupcontaining from 1 to 4 hetero atoms of at least one type selected fromthe group consisting of O, S and N (the heterocyclic group may besubstituted), 1 is from 1 to 4, m is from 0 to 5, n is from 0 to 3, q isfrom 0 to 4, w is from 0 to 2, when 1 is 2 or more, a plurality of R₂may be the same or different, when each of m, n and q is 2 or more, aplurality of R₃ may be the same or different, provided that thefollowing compounds are excluded (1) a compound wherein Q is Qb, Y is═C(R₄)—, and R₁ is alkyl, haloalkyl, alkoxyalkyl, alkylthioalkyl,alkenyl, haloalkenyl, alkynyl, haloalkynyl, —S(O)_(w)R₅ or —CH₂R₉, (2) acompound wherein Q is Qb, Y is ═C(R₄)—, R₁ is —C(═O)R₅, and R₅ is alkylwhich may be substituted, alkenyl which may be substituted, alkynylwhich may be substituted, alkoxy which may be substituted, alkenyloxywhich may be substituted, alkynyloxy which may be substituted,cycloalkyl, cycloalkyloxy, —N(R₇)R₈, phenyl which may be substituted,phenoxy which may be substituted, phenylthio which may be substituted,benzyl which may be substituted, benzyloxy which may be substituted,benzylthio which may be substituted, —J, —O—J or —S—J, (3) a compoundwherein Q is Qb, Y is ═C(R₄)—, R₁ is —C(═S)R₅, and R₅ is —N(R₇)R₈, (4) acompound wherein Q is Qb or Qc, Y is ═N—, R₁ is alkyl or —C(═O)R₅, andR₅ is alkyl, (5) 3-(4-chlorophenyl)-2-phenyl-3-ethoxyacrylonitrile, (6)2-(3,5-dimethoxyphenyl)-3-(2-methoxy-4-methylphenyl)-3-acetoxyacrylonitrile,and (7)2-(3,5-dimethoxyphenyl)-3-(2,6-dimethoxy-4-methylphenyl)-3-acetoxyacrylonitrile;and a process for its production, a pesticide containing it, and a novelintermediate compound useful for its production.

In the formula (I), the substituent for the alkyl which may besubstituted, the alkenyl which may be substituted, the alkynyl which maybe substituted, the alkoxy which may be substituted, the alkenyloxywhich may be substituted, the alkynyloxy which may be substituted, thealkylthio which may be substituted, the alkylsulfinyl which may besubstituted, the alkylsulfonyl which may be substituted, the alkenylthiowhich may be substituted, the alkenylsulfinyl which may be substituted,the alkenylsulfonyl which may be substituted, the alkynylthio which maybe substituted, the alkynylsulfinyl which may be substituted and thealkynylsulfonyl which may be substituted, for each of R₂ and R₃, or thesubstituent for the alkyl which may be substituted, the alkenyl whichmay be substituted, the alkynyl which may be substituted, the alkoxywhich may be substituted, the alkenyloxy which may be substituted, thealkynyloxy which may be substituted, the alkylthio which may besubstituted, the alkenylthio which may be substituted and thealkynylthio which may be substituted, for R₅, may, for example, behalogen, alkoxy, haloalkoxy, alkoxycarbonyl, alkylthio, alkylsulfinyl,alkylsulfonyl, haloalkylthio, haloalkylsulfinyl, haloalkylsulfonyl,amino, monoalkylamino, dialkylamino, nitro or cyano. The number ofsubstituents may be one or more, and when it is more then one, aplurality of substituents may be the same or different.

Further, the substituent for the phenyl which may be substituted, thephenoxy which may be substituted, the phenylthio which may besubstituted, the phenylsulfinyl which may be substituted, thephenylsulfonyl which may be substituted, the benzyl which may besubstituted, the benzyloxy which may be substituted, the benzylthiowhich may be substituted or the benzoyl which may be substituted, foreach of R₂ and R₃, the substituent for the phenyl which may besubstituted, the phenoxy which may be substituted, the phenylthio whichmay be substituted, the benzyl which may be substituted, the benzyloxywhich may be substituted or the benzylthio which may be substituted, forR₅, the substituent for the phenyl which may be substituted, the phenoxywhich may be substituted, the phenylthio which may be substituted, thephenylsulfinyl which may be substituted, the phenylsulfonyl which may besubstituted, the benzyl which may be substituted, the benzyloxy whichmay be substituted, the benzylthio which may be substituted or thebenzoyl which may be substituted, for R₉, or the substituent for theheterocyclic ring for J, may, for example, be halogen, alkyl, haloalkyl,alkoxy, haloalkoxy, nitro, cyano, —S(O)_(w)R₆, amino, monoalkylamino ordialkylamino. The number of substituents may be one or more, and when itis more than one, a plurality of substituents may be the same ordifferent. Here, R₆ is alkyl or haloalkyl, and w is from 0 to 2.

The heterocyclic group for J may, for example, be furyl, thienyl,pyrrolyl, pyrazolyl, imdazolyl, triazolyl, tetrazolyl, oxazolyl,isoxazolyl, thiazolyl, isothiazolyl, pyridyl, pyrimidinyl,1-pyrrolidinyl, 1-piperidinyl or 4-morpholino.

Preferred compounds among the acrylonitrile compounds of the formula (I)or their salts, are as follows.

(a) The acrylonitrile compound or its salt, wherein Q is Qa, Qb or Qc,and each of R₂ and R₃ is halogen, alkyl, haloalkyl, alkoxy, haloalkoxy,alkylthio, alkylsulfinyl, alkylsulfonyl, nitro, cyano, phenyl which maybe substituted by M₁, or phenoxy which may be substituted by M₁, R₅ isalkyl, haloalkyl, alkoxyalkyl, alkylthioalkyl, aminoalkyl,monoalkylaminoalkyl, dialkylaminoalkyl, alkenyl, haloalkenyl, alkynyl,haloalkynyl, alkoxy, haloalkoxy, alkylthio, haloalkylthio,alkoxycarbonylalkylthio, alkenylthio, haloalkenylthio, alkynylthio,haloalkynylthio, cycloalkyl, cycloalkylthio, —N(R₇)R₈, phenyl which maybe substituted by M₁, phenoxy which may be substituted by M₁, phenylthiowhich may be substituted by M₁, benzyl which may be substituted by M₁,benzylthio which may be substituted by M₁, pyridyl which may besubstituted by M₁, 1-pyrrolidinyl, 1-piperidinyl, 4-morpholino,pyridyloxy which may be substituted by M₁, or pyridylthio which may besubstituted by M₁, R₉ is cyano, phenyl which may be substituted by M₁,benzyloxy which may be substituted by M₁, benzoyl which may besubstituted by M₁, pyridyl which may be substituted by M₁, —C(═O)R₁₀,—S(O)_(w)R₁₀ or trimethylsilyl, M₁ is halogen, alkyl, haloalkyl, alkoxy,haloalkoxy, nitro, cyano, —S(O)_(w)R₆, amino, monoalkylamino ordialkylamino, and R₆ is alkyl or haloalkyl. The number of substituentsM₁ may be one or more, and if it is more than one, a plurality of M₁ maybe the same or different.

(b) The acrylonitrile compound or its salt, wherein Q is Qa, Qb or Qc,each of R₂ and R₃ is halogen, alkyl, haloalkyl, alkoxy, haloalkoxy,alkylthio, alkylsulfinyl, alkylsulfonyl, nitro, cyano, phenyl which maybe substituted by M₂, or phenoxy which may be substituted by M₂, R₅ isalkyl, haloalkyl, alkoxyalkyl, alkenyl, haloalkenyl, alkynyl,haloalkynyl, alkoxy, haloalkoxy, alkylthio, haloalkylthio,alkoxycarbonylalkylthio, alkenylthio, haloalkenylthio, alkynylthio,haloalkynylthio, cycloalkyl, cycloalkylthio, —N(R₇)R₈, phenyl which maybe substituted by M₂, phenoxy which may be substituted by M₂, phenylthiowhich may be substituted by M₂, benzyl which may be substituted by M₂,benzylthio which may be substituted by M₂, pyridyl which may besubstituted by M₂, 1-pyrrolidinyl, 1-piperidinyl or 4-morpholino, eachof R₇ and R₈ is hydrogen or alkyl, R₉ is cyano, phenyl which may besubstituted by M₂, benzyloxy which may be substituted by M₂, benzoylwhich may be substituted by M₂, pyridyl which may be substituted by M₂,—C(═O)R₁₀, —S(O)_(w)R₁₀ or trimethylsilyl, M₂ is halogen, alkyl,haloalkyl, alkoxy, haloalkoxy, nitro, cyano or —S(O)_(w)R₆, and R₆ isalkyl. The number of substituents M₂ may be one or more, and when it ismore than one, a plurality of M₂ may be the same or different.

(c) The acrylonitrile compound or its salt according to the above (b),wherein Q is Qa or Qb.

(d) The acrylonitrile compound or its salt according to the above (c),wherein Q is Qa.

(e) The acrylonitrile compound of the above formula (I) or its salt,wherein Q is Qa or Qb, Y is ═C(R₄)—, and R₄ is hydrogen.

(f) The acrylonitrile compound or its salt according to the above (e),wherein Q is Qa.

(g) The acrylonitrile compound or its salt according to the above (e) or(f), wherein R₂ is halogen, alkyl or haloalkyl, and 1 is from 1 to 3.

(h) The acrylonitrile compound or its salt according to the above (e) or(f), wherein R₁ is alkoxyalkyl, —C(═O)R₅, —C(═S)R₅, —S(O)_(w)R₅ or—CH₂R₉, R₂ is halogen, alkyl or haloalkyl, R₃ is halogen or alkyl, R₅ isalkyl, haloalkyl, alkoxyalkyl, alkoxy, haloalkoxy, alkylthio,haloalkylthio, alkoxycarbonylalkylthio, alkenylthio, —N(R₇)R₈, phenylwhich may be substituted by M₃, phenoxy which may be substituted by M₃,phenylthio which may be substituted by M₃, benzyl which may besubstituted by M₃, pyridyl which may be substituted by M₃,1-pyrrolidinyl or 4-morpholino, each of R₇ and R₈ is hydrogen or alkyl,R₉ is phenyl, M₃ is halogen, alkyl or alkoxy, 1 is from 1 to 3, m isfrom 0 to 3, n is from 0 to 1, and w is from 1 to 2. The number ofsubstituents M₃ may be one or more, and when it is more than one, aplurality of M₃ may be the same or different.

(i) The acrylonitrile compound of the formula (I) or its salt, whereinthe formula (I) is the formula (I-1);

wherein Q is Qa or Qb, R_(2a) is haloalkyl, R_(2b) is halogen, alkyl orhaloalkyl, d is from 0 to 2, m is from 0 to 3, and n is from 0 to 1.When d is 2, two R_(2b) may be the same or different.

(j) The acrylonitrile compound or its salt according to the above (i),wherein Q is Qa.

(k) The acrylonitrile compound or its salt according to the above (i),wherein d is 0.

(l) The acrylonitrile compound or its salt according to the above (j),wherein d is 0.

(m) The acrylonitrile compound or its salt according to the above (i),(j), (k) or (l), wherein R₁ is alkoxyalkyl, —C(═O)R₅, —C(═S)R₅,—S(O)_(w)R₅ or —CH₂R₉, R₂ is halogen, alkyl or haloalkyl, R₃ is halogenor alkyl, R₅ is alkyl, haloalkyl, alkoxyalkyl, alkoxy, haloalkoxy,alkylthio, haloalkylthio, alkoxycarbonylalkylthio, alkenylthio,—N(R₇)R₈, phenyl which may be substituted by M₃, phenoxy which may besubstituted by M₃, phenylthio which may be substituted by M₃, benzylwhich may be substituted by M₃, pyridyl which may be substituted by M₃,1-pyrrolidinyl or 4-morpholino, each of R₇ and R₈ is hydrogen or alkyl,R₉ is phenyl, M₃ is halogen, alkyl or alkoxy, 1 is from 1 to 3, m isfrom 0 to 3, n is from 0 to 1, and w is from 1 to 2.

In the compounds of the formula (I) or (a) to (m), the alkyl or alkylmoiety contained in R₁, R₂, R_(2a), R_(2b), R₃, R₄, R₅, R₆, R₇, R₈, R₁₀,M₁, M₂ or M₃, May, for example, be straight chain or branched one havingfrom 1 to 6 carbon atoms such as methyl, ethyl, propyl, isopropyl,butyl, tert-butyl, pentyl or hexyl. The alkenyl, alkynyl, alkenyl moietyor alkynyl moiety contained in R₁, R₂, R₃ or R₅, may, for example, bestraight chain or branched one having from 2 to 6 carbon atoms, such asvinyl, allyl, butadienyl, isopropenyl, ethynyl, propinyl or2-penten-4-enyl. The cycloalkyl or cycloalkyl moiety contained in R₅,may, for example, be one having from 3 to 6 carbon atoms, such ascyclopropyl, cyclopentyl or cyclohexyl.

In the compounds of the formula (I) or (a) to (m), the halogen containedin R₁, R₂, R_(2a), R_(2b), R₃, R₄, R₆,M₁, M₂ or M₃, or the halogen as asubstituent, may be fluorine, chlorine, bromine or iodine. The number ofhalogens as substituents may be one or more, and when it is more thanone, a plurality of halogens may be the same or different.

The acrylonitrile compound of the formula (I) is capable of forming asalt. Such a salt may be any salt so long as it is acceptable foragriculture. For example, it may be an inorganic salt such as ahydrochloride, a sulfate or a nitrate, or an organic salt such as anacetate or a methanesulfonate.

The acrylonitrile compound of the formula (I) may have geometricalisomers (E-isomer and Z-isomer). The present invention includes suchisomers and their mixtures.

The acrylonitrile compound of the formula (I) or its salt (hereinafterreferred to simply as the compound of the present invention) can beproduced, for example, by reactions (A) to (C) and by a usual processfor producing a salt.

Now, the reaction (A) will be described.

In the reaction (A), Q, Y, R₁, R₂, 1 and the formula (I) are as definedabove, and X is halogen.

The reaction (A) is carried out usually in the presence of a base. Assuch a base, one or more may suitably be selected for use from e.g.alkali metals such as sodium and potassium; alkali metal alcoholatessuch as potassium tertiary butoxide; carbonates such as potassiumcarbonate and sodium carbonate; bicarbonates such as potassiumbicarbonate and sodium bicarbonate; metal hydroxides such as potassiumhydroxide and sodium hydroxide; metal hydrides such as potassium hydrideand sodium hydride; and tertiary amines such a trimethylamine,triethylamine, pyridine and 4-dimethylaminopyridine.

The reaction (A) may be carried out, if necessary, in the presence of asolvent. Such a solvent may be any solvent so long as it is inert to thereaction. For example, one or more may be suitably selected for use frome.g. aromatic hydrocarbons such as benzene, toluene, xylene andchlorobenzene; cyclic or non-cyclic aliphatic hydrocarbons such ascarbon tetrachloride, methyl chloride, chloroform, dichloromethane,dichloroethane, trichloroethane, hexane and cyclohexane; ethers such asdioxane, tetrahydrofuran and diethyl ether; esters such as methylacetate and ethyl acetate; dipolar aprotic solvents such asdimethylsulfoxide, sulfolane, dimethylacetamide, dimethylformamide,N-methylpyrrolidone and pyridine; nitriles such as acetonitrile,propionitrile and acrylonitrile; ketones such as acetone and methylethyl ketone; tertiary amines such as trimethylamine and triethylamine;and water.

For the reaction (A), a catalyst such as 4-dimethylaminopyridine may beused, as the case requires.

The reaction temperature for the reaction (A) is usually from −80 to+150° C., preferably from −50 to +120° C., and the reaction time isusually from 0.1 to 48 hours, preferably from 0.5 to 24 hours.

In a case where in the formula (I), R₁ is methyl:

The reaction (B) will be described in detail. In the reaction (B), Q, Y,R₂, 1 and the formula (II) are as defined above.

The reaction (B) is carried out usually in the presence of a solvent. Assuch a solvent, one or more may suitably be selected for use from e.g.aromatic hydrocarbons such as benzene, toluene, xylene andchlorobenzene; cyclic or non-cyclic aliphatic hydrocarbons such ascarbon tetrachloride, methyl chloride, chloroform, dichloromethane,dichloroethane, trichloroethane, hexane and cyclohexane; ethers such asdioxane, tetrahydrofuran and diethyl ether; esters such as methylacetate and ethyl acetate; nitriles such as acetonitrile, propionitrileand acrylonitrile; and ketones such as acetone and methyl ethyl ketone.

The reaction temperature for the reaction (B) is usually from 0 to 100°C., preferably from 0 to 50° C., and the reaction time is usually from0.1 to 24 hours, preferably from 0.1 to 12 hours.

In a case where in the formula (I), R₁ is —C(═O)R₅, —C(═S)R₅ or—S(O)_(w)R₅:

The reaction (C) will be described. In the reaction (C), Q, Y, R₂, R₅, 1and the formula (II) are as defined above, T is —C(═O)—, —C(═S)— or—S(O)_(w)—, G is hydrogen, Li, MgBr, MgCl or Mgl, and R_(1a) is—C(═O)R₅, —C(═S)R₅ or —S(O)_(w)R₅ (wherein R₅ and w are as definedabove).

The first step in the reaction (C) is carried out, if necessary, in thepresence of a base. As such a base, one or more may suitably be selectedfor use from e.g. tertiary amines such as trimethylamine, triethylamine,pyridine and 4-dimethylaminopyridine.

The first step of the reaction (C) is carried out usually in thepresence of a solvent. Such a solvent may be any solvent so long as itis inert to the reaction. For example, one or more may suitably selectedfor use from e.g. aromatic hydrocarbons such as benzene, toluene, xyleneand chlorobenzene; cyclic or non-cyclic aliphatic hydrocarbons such ascarbon tetrachloride, methyl chloride, chloroform, dichloromethane,dichloroethane, trichloroethane, hexane and cyclohexane; ethers such asdioxane, tetrahydrofuran and diethyl ether; and esters such as methylacetate and ethyl acetate.

The reaction temperature for the first step of the reaction (C) isusually from −80 to +150° C., preferably from −50 to +80° C., and thereaction time is usually from 0.1 to 48 hours, preferably from 0.5 to 24hours. The compound of the formula (V) prepared by the first step of thereaction (C) is a novel intermediate compound useful in the presentinvention.

The second step of the reaction (C) is carried out, if necessary, in thepresence of a base. As such a base, one or more may suitably be selectedfor use from e.g. carbonates such as potassium carbonate and sodiumcarbonate; and tertiary amines such as trimethylamine, triethylamine,pyridine and 4-dimethylaminopyridine.

The second step of the reaction (C) is carried out usually in thepresence of a solvent. Such a solvent may be any solvent so long as itis inert to the reaction. For example, one or more may suitably beselected for use from e.g. aromatic hydrocarbons such as benzene,toluene, xylene and chlorobenzene; cyclic or non-cyclic aliphatichydrocarbons such as carbon tetrachloride, methyl chloride, chloroform,dichloromethane, dichloroethane, trichloroethane, hexane andcyclohexane; ethers such as dioxane, tetrahydrofuran and diethyl ether;esters such as methyl acetate and ethyl acetate; nitriles such asacetonitrile, propionitrile and acrylonitrile; and ketones such asacetone and methyl ethyl ketone.

The reaction temperature for the second step of the reaction (C) isusually from −80 to +150° C., preferably from −80 to +80° C., and thereaction time is usually from 0.1 to 48 hours, preferably from 0.5 to 24hours.

The compounds of the formula (II) in the above reactions (A) to (C) areintermediate compounds useful for producing the compounds of the presentinvention, and novel compounds are included therein.

The compound of the formula (II) may form a salt. Such a salt may be anysalt so long as it is agriculturally acceptable. For example, it may bean inorganic salt such as a hydrochloride, a sulfate or a nitrate; anorganic salt such as an acetate or a methane sulfonate, an alkali metalsalt such as a sodium salt or a potassium salt; an alkaline earth metalsalt such as a magnesium salt or a calcium salt; or a quaternaryammonium salt such as dimethylammonium or triethylammonium.

The compound of the formula (II) has geometrical isomers (E-isomer andZ-isomer). The present invention includes such isomers and mixturesthereof. The compound of the formula (II) may also be present in theform of tautomers represented by the following formula:

The present invention includes such tautomers and mixtures thereof.

Further, the compounds of the formula (II) include those which exhibitpesticidal activities.

The compound of the formula (II) or its salt may be prepared e.g. byreactions (D) to (F), or by a conventional method for producing a salt.

The reaction (D) will be described. In the reaction (D), Q, Y, R₂, 1 andthe formula (II) are as defined above, and Z₁ is alkoxy.

The reaction (D) is carried out usually in the presence of a base and asolvent. As such a base, one or more may suitably be selected for usefrom e.g. alkali metals such as sodium and potassium; alkali metalalcoholates such as sodium methylate, sodium ethylate and potassiumtertiary butoxide; metal hydrides such as potassium hydride and sodiumhydride; and organic lithium such as methyllithium, butyllithium,tert-butyllithium and phenyllithium. As the solvent, one or more maysuitably selected for use from e.g. aromatic hydrocarbons such asbenzene, toluene, xylene and chlorobenene; ethers such as dioxane,tetrahydrofuran and diethyl ether; and alcohols such as methanol,ethanol, propanol and tert-butanol.

The reaction temperature for the reaction (D) is usually from −80 to+150° C., preferably from −50 to +120° C., and the reaction time isusually from 0.1 to 48 hours, preferably from 0.5 to 24 hours.

In a case where in the formula (II), Q is Qa:

The reaction (E) will be described as follows. In the reaction (E), Qa,Y, R₂ and 1 are as defined above, and Z₂ is halogen.

The first step of the reaction (E) is carried out usually in thepresence of a base. As such a base, one or more may suitably be selectedfor use from e.g. alkali metals such as sodium and potassium; alkalimetal alcoholates such as sodium methylate, sodium ethylate andpotassium tertiary butoxide; carbonates such as potassium carbonate andsodium carbonate; bicarbonates such as potassium bicarbonate and sodiumbicarbonate; metal hydroxides such as potassium hydroxide and sodiumhydroxide, metal hydrides such as potassium hydride and sodium hydride;amines such as monomethylamine, dimethylamine and trimethylamine; andpyridines such as pyridine and 4-dimethylaminopyridine.

The first step of the reaction (E) is carried out, if necessary, in thepresence of a solvent. Such a solvent may be any solvent so long as itis inert to the reaction. For example, one or more may suitably beselected for use from e.g. aromatic hydrocarbons such as benzene,toluene, xylene and chlorobenene; cyclic or non-cyclic aliphatichydrocarbons such as carbon tetrachloride, methyl chloride, chloroform,dichloromethane, dichloroethane, trichloroethane, hexane andcyclohexane; ethers such as dioxane, tetrahydrofuran and diethyl ether;esters such as methyl acetate and ethyl acetate; dipolar aproticsolvents such as dimethylsulfoxide, sulfolane, dimethylacetamide,dimethylformamide, N-methylpyrrolidone and pyridine; ketones such asacetone and methyl ethyl ketone; amines such as monomethylamine,dimethylamine and triethylamine; and water.

For the first step of the reaction (E), a catalyst such as4-dimethylaminopyridine may be used, as the case requires.

The reaction temperature for the first step of the reaction (E) isusually from −80 to +150° C., preferably from −50 to +120° C., and thereaction time is usually from 0.1 to 48 hours, preferably from 0.5 to 24hours.

The compound of the formula (X) prepared by the first step of thereaction (E) is a novel intermediate compound useful in the presentinvention and at the same time includes a compound of the presentinvention. Accordingly, the compound of the present invention can beprepared also by the first step of the reaction (E).

The second step of the reaction (E) is a hydrolysis reaction which iscarried out usually in the presence of a base or an acid. As the base,one or more may suitably be selected for use from e.g. carbonates suchas potassium carbonate and sodium carbonate; metal hydroxides such aspotassium hydroxide and sodium hydroxide; and amines such asmonomethylamine, dimethylamine and triethylamine. As the acid, one ormore may suitably be selected for use from e.g. inorganic acids such ashydrochloric acid and sulfuric acid; and organic acids such as aceticacid.

The second step of the reaction (E) is carried out, if necessary, in thepresence of a solvent. Such a solvent may be any solvent so long as itis inert to the reaction. For example, one or more may suitably beselected for use from e.g. nitriles such as acetonitrile, propionitrileand acrylonitrile; alcohols such a methanol, ethanol, propanol andtert-butanol; organic acids such as acetic acid and propionic acid;aqueous ammonia; and water.

The reaction temperature for the second step of the reaction (E) isusually from 0 to 100° C., preferably from 0 to 50° C., and the reactiontime is usually from 0.1 to 48 hours, preferably from 0.5 to 24 hours.

In a case where in the formula (II), Q is Qc:

The reaction (F) will be described as follows. In the reaction (F), Qc,Y, R₂, 1 and the formula (IX) are as defined above.

The reaction (F) is carried out in accordance with the first step of thereaction (E).

Among compounds of the formula (II) thus prepared, the followingcompounds are particularly useful and novel.

Compounds of the formula (II-1) or their salts:

wherein Q, R_(2a), R_(2b) and d are as defined above, provided that whenQ is Qc, (1) q is not 0, or (2) R₃ is not alkyl.

Particularly preferred compounds among the compounds of the formula(II-1) are as follows.

(n) A compound of the above formula (II-1) wherein Q is Qa or Qb, or itssalts.

(o) A compound of the above formula (II-1) wherein Q is Qa, or its salt.

(p) A compound of the above formula (II-1), (n) or (o) wherein d is 0,or its salt.

The compounds of the present invention are useful as active ingredientsfor pesticides. They are particularly useful as active ingredients ofpesticides such as an insecticide, a miticide, a nematicide, a soilpesticide, a fungicide and a marine antifouling agent.

Preferred embodiments of pesticides containing the compounds of thepresent invention will now be described. Firstly, pesticides such as aninsecticide, a miticide, a nematicide, a soil pesticide and a fungicide,will be described.

The pesticides containing the compounds of the present invention areuseful as an insecticide, a miticide, a nematicide and a soil pesticide(hereinafter referred to as insect pest control agents), and they areeffective for controlling plant parasitic mites such as two-spottedspider mite (Tetranychus urticae), carmine spider mite (Tetranychuscinnabarinus), kanzawa spider mite (Tetranychus kanzawai), citrus redmite (Panonychus citri), European red mite (Panonychus ulmi), broad mite(Polyphagotarsonemus latus), pink citrus rust mite (Aculops pelekassi)and bulb mite (Rhizoqlyphus echinopus); animal parasitic mites such asIxodes; aphids such as green peach aphid (Myzus persicae) and cottonaphid (Aphis gossypii); agricultural insect pests such as diamondbackmoth (Plutella xylostella), cabbage armyworm (Mamestra brassicae),common cutworm (Spodoptera litura), codling moth (Laspeyresiapomonella), bollworm (Heliothis zea), tobacco budworm (Heliothisvirescens), gypsy moth (Lymantria dispar), rice leafroller(Cnaphalocrocis medinalis), Adoxophyes sp., colorado potato beetle(Leptinotarsa decemlineata), cucurbit leaf beetle (Aulacophorafemoralis), boll weevil (Anthonomus grandis), planthoppers, leafhoppers(Circulifer sp.), scales, bugs, whiteflies, thrips, grasshoppers,anthomyiid flies, scarabs, black cutworm (Agrotis ipsilon), cutworm(Agrotis segetum) and ants; plant parasitic nematodes such as root-knotnematodes, cyst nematodes, root-lesion nematodes, rice white-tipnematode (Aphelenchoides besseyi), strawberry bud nematode(Nothotylenchus acris), pine wood nematode (Bursaphelenchus lignicolus);gastropods such as slugs and snails; soil pests such as isopods such aspillbugs (Armadilidium vulgare) and pillbugs (Porcellio scaber);hygienic insect pests such as tropical rat mite (Ornithonyssus bacoti),cockroachs, housefly (Musca domestica) and house mosquto (Culexpipiens); stored grain insect pests such as angoumois grai moth(Sitotroga cerealella), adzuki bean weevil (Callosobruchus chinensis),red flour beetle (Tribolium castaneum) and mealworms; household goodsinsect pests such as casemaking clothes moth (Tinea pellionella), blackcarpet beetle (Anthrenus scrophularidae) and subterranean termites;domestic mites such as mold mite (Tyrophagus putrescentiae),Dermatophagoides farinae and Chelacaropsis moorei; and others such asfleas, lice and flies, which are parasitic to e.g. domestic animals.Among them, the insect pest control agents containing the compounds ofthe present invention are particularly effective for controlling plantparasitic mites, animal parasitic mites, agricultural insect pests,hygienic insect pests, household goods insect pests, domestic mites orthe like. Further, they are effective against insect pests havingacquired resistance to organophosphorus, carbamate and/or syntheticpyrethroid insecticides. Moreover, the compounds of the presentinvention have excellent systemic properties, and by the application ofthe compounds of the present invention to solid treatment, not onlynoxious insects, noxious mites, noxious nematodes, noxious gastropodsand noxious isopods in soil but also foliage pests can be controlled.

Further, the pesticides containing compounds of the present inventionare useful as fungicides. For example, they are effective forcontrolling diseases, such as blast (Pyricularia oryzae), sheath blight(Rhizoctonia solani) and brown spot (Cochliobolus miyabeanus) againstrice; powdery mildew (Erysiphe graminis), scab (Gibberella zeae), rust(Puccinia striiformis, P. coronata, P. graminis, P. recondita, P.hordei), snow blight (Typhula sp., Micronectriella nivalis), loose smut(Ustilago tritici, U. nuda), eye spot (Pseudocercosporellaherpotrichoides), leaf blotch (Septoria tritici) and glume blotch(Leptosphaeria nodorum) against cereals; melanose (Diaporthe citri) andscab (Elsinoe fawcetti) against citrus; blossom blight (Sclerotiniamali), powdery mildew (Podosphaera leucotricha), alternaria blotch(Alternaria mali) and scab (Venturia inaequalis) against apples; scab(Venturia nashicola) and black spot (Alternaria kikuchiana) againstpears; brown rot (Monilinia fructicola), scab (Cladosporium carpophilum)and phomopsis rot (Phomopsis sp.) against peaches; anthracnose (Elsinoeampelina) ripe rot (Glomerella cingulata), powdery mildew (Uncinulanecator) and downy mildew (Plasmopara viticola) against grapes;anthracnose (Gloeosporium kaki) and angular leaf spot (Cercospora kaki)against Japanese persimon; anthracnose (Colletotrichum lagenarium),powdery mildew (Sphaerotheca fuliginia), gummy stem blight(Mycosphacrella melonis) and downy mildew (Pseudopernospora cubensis)against cucurbits; early blight (Alternaria solani), leaf mold(Cladosporium fulvum) and late blight (Phytophthora infestans) againsttomatoes; alternaria leaf spot (Alternaria brassicae) against crucifer;early blight (Alternaria solani) and late blight (Phytophthorainfestans) against potatoes; powdery mildew (Sphaerotheca humuli)against strawberry; gray mold (Botrytis cinerea) and sclerotinial rot(Sclerotinia sclerotiorum) against various crop plants. Further, theyare effective also for controlling soil diseases brought about by plantpathogenic fungi such as Fusarium sp., Pythium sp., Rhizoctonia sp.,Verticillium sp., and Plasmodiophora sp.

Another preferred embodiments of the pesticides containing compounds ofthe present invention may be agricultural and horticultural pesticideswhich collectively control the above-mentioned plant parasitic mites,agricultural insect pests, plant parasitic nematodes, gastropods, soilpests, various diseases and various soil diseases.

The pesticide such as the insect pests control agent or the fungicidecontaining the compound of the present invention, is usually formulatedby mixing the compound with various agricultural adjuvants and used inthe form of a formulation such as a dust, granules, water-dispersiblegranules, a wettable powder, a water-based suspension concentrate, anoil-based suspension concentrate, water soluble granules, anemulsifiable concentrate, a paste, an aerosol or an ultra low-volumeformulation. However, so long as it is suitable for the purpose of thepresent invention, it may be formulated into any type of formulationwhich is commonly used in this field. Such agricultural adjuvantsinclude solid carriers such as diatomaceous earth, slaked lime, calciumcarbonate, talc, white carbon, kaoline, bentonite, a mixture ofkaolinite and sericite, clay, sodium carbonate, sodium bicarbonate,mirabilite, zeolite and starch; solvents such as water, toluene, xylene,solvent naphtha, dioxane, acetone, isophorone, methyl isobutyl ketone,chlorobenzene, cyclohexane, dimethylsulfoxide, dimethylformamide,dimethylacetamide, N-methyl-2-pyrrolidone, and alcohol; anionicsurfactants and spreaders such as a salt of fatty acid, a benzoate, analkylsulfosuccinate, a dialkylsulfosuccinate, a polycarboxylate, a saltof alkylsulfuric acid ester, an alkyl sulfate, an alkylaryl sulfate, analkyl diglycol ether sulfate, a salt of alcohol sulfuric acid ester, analkyl sulfonate, an alkylaryl sulfonate, an aryl sulfonate, a ligninsulfonate, an alkyldiphenyl ether disulfonate, a polystyrene sulfonate,a salt of alkylphosphoric acid ester, an alkylaryl phosphate, astyrylaryl phosphate, a salt of polyoxyethylene alkyl ether sulfuricacid ester, a polyoxyethylene alkylaryl ether sulfate, a salt ofpolyoxyethylene alkylaryl ether sulfuric acid ester, a polyoxyethylenealkyl ether phosphate, a salt of polyoxyethylene alkylaryl phosphoricacid ester, and a salt of a condensate of naphthalene sulfonate withformalin; nonionic surfactants and spreaders such as a sorbitan fattyacid ester, a glycerin fatty acid ester, a fatty acid polyglyceride, afatty acid alcohol polyglycol ether, acetylene glycol, acetylenealcohol, an oxyalkylene block polymer, a polyoxyethylene alkyl ether, apolyoxyethylene alkylaryl ether, a polyoxyethylene styrylaryl ether, apolyoxyethylene glycol alkyl ether, a polyoxyethylene fatty acid ester,a polyoxyethylene sorbitan fatty acid ester, a polyoxyethylene glycerinfatty acid ester, a polyoxyethylene hydrogenated castor oil, and apolyoxypropylene fatty acid ester; and vegetable and mineral oils suchas olive oil, kapok oil, castor oil, palm oil, camellia oil, coconutoil, sesame oil, corn oil, rice bran oil, peanut oil, cottonseed oil,soybean oil, rapeseed oil, linseed oil, tung oil, and liquid paraffins.Such adjuvants may be selected for use among those known in this field,so long as the purpose of the present invention can thereby beaccomplished. Further, various additives which are commonly used, suchas a filler, a thickener, an anti-settling agent, an anti-freezingagent, a dispersion stabilizer, a phytotoxicity reducing agent, and ananti-mold agent, may also be employed.

The weight ratio of the compound of the present invention to the variousagricultural adjuvants is usually from 0.001:99.999 to 95:5, preferablyfrom 0.005:99.995 to 90:10.

In the actual application of such a formulation, it may be used as itis, or may be diluted to a predetermined concentration with a diluentsuch as water, and various extenders may be added thereto, as the caserequires.

The application of the pesticide such as the insect pest control agentor the fungicide containing the compound of the present invention cannot generally be defined, as it varies depending upon the weatherconditions, the type of the formulation, the application season, theapplication site or the types or degree of outbreak of the pest insects.However, it is usually applied in a concentration of the activeingredient being from 0.05 to 800,000 ppm, preferably from 0.5 to500,000 ppm, and the dose per unit area is such that the compound of thepresent invention is from 0.05 to 10,000 g, preferably from 1 to 5,000g, per hectare. The application of the insect pest control agent as apreferred embodiment of the pesticide containing the compound of thepresent invention, can not generally be defined, as it varies dependingupon various conditions as mentioned above, but is usually carried outin a concentration of the active ingredient being from 0.1 to 500,000ppm, preferably from 1 to 100,000 ppm, and the dose per unit area issuch that the compound of the present invention is from 0.1 to 10,000 g,preferably from 10 to 1,000 g, per hectare. The application of thefungicide can not generally be defined, as it varies depending uponvarious conditions as described above, but is usually carried out in aconcentration of the active ingredient being from 0.1 to 500,000 ppm,preferably from 1 to 100,000 ppm, and the dose per unit area is suchthat the compound of the present invention is from 0.1 to 10,000 g,preferably from 10 to 1,000 g, per hectare. Further, agricultural andhorticultural pesticides as another preferred embodiment of pesticidescontaining the compounds of the present invention may be applied inaccordance with the above-described application of insect pest controlagents and fungicides. The present invention includes such a method forcontrolling insect pests by such applications.

Various formulations of pesticides such as insect pest control agents orfungicides containing the compounds of the present invention or theirdiluted compositions may be applied by conventional methods forapplication which are commonly employed, such as spraying (e.g.spraying, jetting, misting, atomizing, powder or grain scattering ordispersing in water), soil application (e.g. mixing or drenching),surface application (e.g. coating, powdering or covering) orimpregnation to obtain poisonous feed. Further, it is possible to feeddomestic animals with a food containing the above active ingredient andto control the outbreak or growth of pests, particularly insect pests,with their excrements. Furthermore, the active ingredient may also beapplied by a so-called ultra low-volume application method. In thismethod, the composition may be composed of 100% of the activeingredient.

Further, the pesticides such as insect pest control agents or fungicidescontaining compounds of the present invention may be mixed with or maybe used in combination with other agricultural chemicals, fertilizers orphytotoxicity-reducing agents, whereby synergistic effects or activitiesmay sometimes be obtained. Such other agricultural chemicals include,for example, a herbicide, an insecticide, a miticide, a nematicide, asoil pesticide, a fungicide, an antivirus agent, an attractant, anantibiotic, a plant hormone and a plant growth regulating agent.Especially, with a mixed pesticide having a compound of the presentinvention mixed with or used in combination with one or more activecompounds of other agricultural chemicals, the application range, theapplication time, the pesticidal activities, etc. may be improved topreferred directions. The compound of the present invention and theactive compounds of other agricultural chemicals may separately beformulated so that they may be mixed for use at the time of application,or they may be formulated together. The present invention includes sucha mixed pesticidal composition.

The mixing ratio of the compound of the present invention to the activecompounds of other agricultural chemicals can not generally be defined,since it varies depending upon the weather conditions, the types offormulations, the application time, the application site, the types ordegree of outbreak of insect pests, etc., but it is usually within arange of from 1:300 to 300:1, preferably from 1:100 to 100:1, by weight.Further, the dose for the application is such that the total amount ofthe active compounds is from 0.1 to 5,000 g, preferably from 10 to 3,000g, per hectare. The present invention includes a method for controllinginsect pests by an application of such a mixed pesticide composition.

The active compounds of insect pest control agents such as insecticides,miticides, nematicides or soil pesticides in the above-mentioned otheragricultural chemicals, include, for example, (by common names, some ofthem are still in an application stage) organic phosphate compounds suchas Profenofos, Dichlorvos, Fenamiphos, Fenitrothion, EPN, Diazinon,Chlorpyrifos-methyl, Acephate, Prothiofos, Fosthiazate and Phosphocarb;carbamate compounds such as Carbaryl, Propoxur, Aldicarb, Carbofuran,Thiodicarb, Methomyl, Oxamyl, Ethiofencarb, Pirimicarb, and Fenobucarb;nereistoxin derivatives such as Cartap, and Thiocyclam; organic chlorinecompounds such as Dicofol, and Tetradifon; organometallic compounds suchas Fenbutatin Oxide; pyrethroid compounds such as Fenvalerate,Permethrin, Cypermethrin, Deltamethrin, Cyhalothrin, Tefluthrin, andEthofenprox; benzoylurea compounds such as Diflubenzuron,Chlorfluazuron, Teflubenzuron, and Novaluron; juvenile hormone-likecompounds such as Methoprene; pyridazinone compounds such as Pyridaben;pyrazole compounds such as Fenpyroximate, Fipronil, and Tebufenpyrad;neonicotinoids such as Imidacloprid, Nitenpyram, Acetamiprid, Diacloden,and Thiacloprid; hydrazine compounds such as Tebufenozide,Methoxyfenozide, and Chromafenozide; dinitro compounds; organic sulfurcompounds; urea compounds; triazine compounds; hydrazone compounds; andother compounds, such as Buprofezin, Hexythiazox, Amitraz,Chlordimeform, Silafluofen, Triazamate, Pymetrozine, Pyrimidifen,Chlorfenapyr, Indoxacarb, Acequinocyl, Etoxazole, and Cyromazin.Further, BT agents, microbial agricultural chemicals such as insectviruses, or antibiotics such as Avermectin, Milbemycin and Spinosad, maybe used in admixture or in combination.

The active compounds of fungicides among the above-mentioned otheragricultural chemicals include, for example, (by common names, some ofwhich are still in an application stage) pyrimidinamine compounds suchas Mepanipyrim, Pyrimethanil, and Cyprodinil; azole compounds such asTriadimefon, Bitertanol, Triflumizole, Etaconazole, Propiconazole,Penconazole, Flusilazole, Myclobutanil, Cyproconazole, Terbuconazole,Hexaconazole, Furconazole-cis, Prochloraz, Metconazole, Epoxiconazole,and Tetraconazole; quinoxaline compounds such as Quinomethionate;dithiocarbamate compounds such as Maneb, Zineb, Mancozeb, Polycarbamate,Propineb; organic chlorine compounds such as Fthalide, Chlorothalonil,and Quintozene; imidazole compounds such as Benomyl, Thiophanate-Methyl,Carbendazim, and4-chloro-2-cyano-1-dimethylsulfamoyl-5-(4-methylphenyl)imidazole;pyridinamine compounds such as Fluazinam; cyanoacetamide compounds suchas Cymoxanil; phenylamide compounds such as Metalaxyl, Oxadixyl,Ofurace, Benalaxyl, Furalaxyl, and Cyprofuram; sulfenic acid compoundssuch as Dichlofluanid; copper compounds such as cupric hydroxide, andOxine Copper; isoxazole compounds such as Hydroxyisoxazole;organophosphorus compounds such as Fosetyl-Al, Tolcofos-Methyl, S-benzylO,O-diisopropylphosphorothioate, O-ethyl S,S-diphenylphosphorodithioate,and aluminumethylhydrogen phosphonate; N-halogenothioalkyl compoundssuch as Captan, Captafol, and Folpet; dicarboximide compounds such asProcymidone, Iprodione, and Vinclozolin; benzanilide compounds such asFlutolanil, and Mepronil; piperazine compounds such as Triforine;pyrizine compounds such as Pyrifenox; carbinol compounds such asFenarimol; and Flutriafol; piperidine compounds such as Fenpropidine;morpholine compounds such as Fenpropimorph; organotin compounds such asFentin Hydroxide, and Fentin Acetate; urea compounds such as Pencycuron;cinnamic acid compounds such as Dimethomorph; phenylcarbamate compoundssuch as Diethofencarb; cyanopyrrole compounds such as Fludioxonil, andFenpiclonil; β-methoxyacrylate compounds such a Azoxystrobin,Kresoxim-Methyl, and Metominofen; oxazolidinedione compounds such asFamoxadone; anthraquinone compounds; crotonic acid compounds;antibiotics; and other compounds, such as Isoprothiolane, Tricyclazole,Pyroquilon, Diclomezine, Pro. benazole, Quinoxyfen, PropamocarbHydrochloride and Spiroxamine.

Now, pesticides like marine antifouling agents will be described.

The marine antifouling agents containing the compounds of the presentinvention are effective for controlling noxious marine organisms againstships or underwater structures (such as harbour structures, buoys,pipelines, bridges, submarine bases, seabed oilfield drillinginstallations, water conduits for power plants, fixed shore nets andculturing nets). Specifically, they are effective for preventing theattachment and propagation of plants such as green algae and brownalgae, animals such as a barnacle, a serpla, an ascidian, a sea musseland an oyster, various bacteria called slime, and aquatics such as moldand a diatom, at the bottoms of ships or on underwater structures.

The marine antifouling agents containing the compounds of the presentinvention provide antifouling and antislime properties over a longperiod of time and exhibit excellent effects for preventing theattachment and propagation of noxious marine organisms against ships orunderwater structures.

The marine antifouling agents containing the compounds of the presentinvention are usually formulated and used in the form of paintcompositions. However, they may be formulated and used in other forms(such as solutions, emulsifiable concentrates, or pellets) as the caserequires. Paint vehicles to be used for formulating the compounds of thepresent invention into coating compositions, may be resin vehicles whichare commonly used. For example, a vinyl chloride resin, a vinylchloride-vinyl acetate copolymer, a vinyl chloride-vinyl isobutyl ethercopolymer, a chlorinated rubber resin, a chlorinated polyethylene resin,a chlorinated polypropylene resin, an acrylic resin, a styrene-butadieneresin, a polyester resin, an epoxy resin, a phenol resin, a syntheticrubber, a silicone rubber, a silicone resin, a petroleum resin, a oiland fat resin, a rosin ester resin, a rosin soap or rosin, may bementioned. Further, as a vehicle having antifouling properties, anacrylic copolymer resin composition containing, as constituting units,an organotin compound salt of an unsaturated mono- or di-carboxylicacid, obtainable by a condensation reaction of (meth)acrylic acid withan organotin compound such as bis(tributyltin)oxide or triphenyltinhydroxide, or a resin containing a metal element such as copper, zinc ortellurium in its side chains, may, for example, be used.

When the compound of the present invention is formulated as a coatingcomposition, the blend proportion is adjusted so that the compound ofthe present invention will be contained in an amount of from 0.1 to 60wt %, preferably from 1 to 40 wt %, based on the entire coatingcomposition.

The coating composition containing the compound of the present inventioncan be prepared by using e.g. a ball mill, a pebble mill, a roll mill ora sand grinder in accordance with a method which is well known in thefield of preparing coating materials. Further, the above coatingcomposition may contain a plasticizer, a coloring pigment, an extenderpigment, an organic solvent, etc. which are commonly used in this field.

The coating composition containing the compound of the present inventionmay further contain any other known inorganic or organic antifoulingagent, as the case requires. Such an antifouling agent includes, forexample, cuprous oxide, copper rhodanide, copper hydroxide, coppernaphthenate, metallic copper and various tin compounds anddithiocarbamic acid derivatives, such as tetramethylthiuram monosulfide,tetramethylthiuram disulfide, zinc bis-(dimethyldithiocarbamate), zincethylene-bis(dithiocarbamate), manganese ethylene-bis(dithiocarbamate),and copper bis(dimethyldithiocarbamate).

As described in the foregoing, the compound of the present invention orthe compound of the formula (II) as its intermediate, is effective as anactive ingredient of a pesticide. Various embodiments thereof will besummarized as follows.

(1) A pesticide containing a compound of the above formula (I) or (II),or its salt, as an active ingredient, or a method for controlling pestsby employing such a compound.

(2) An agricultural and horticultural pesticide containing a compound ofthe above formula (I) or (II), or its salt, as an active ingredient, ora method for controlling pests in an agricultural and horticulturalfield by employing such a compound.

(3) An insect pest control agent containing a compound of the aboveformula (I) or (II), or its salt, as an active ingredient, or a methodfor controlling pests by employing such a compound.

(4) An insecticide containing a compound of the above formula (I) or(II), or its salt, as an active ingredient, or a method for controllingnoxious insects by employing such a compound.

(5) A miticide containing a compound of the above formula (I) or (II),or its salt, as an active ingredients, or a method for controlling mitesby employing such a compound.

(6) A nematicide containing a compound of the above formula (I) or (II),or its salt, as an active ingredient, or a method for controllingnematodes by employing such a compound.

(7) A soil pesticide containing a compound of the above formula (I) or(II), or its salt, as an active ingredient, or a method for controllingsoil pests by employing such a compound.

(8) A fungicide containing a compound of the above formula (I) or (II),or its salt, as an active ingredient, or a method for controlling fungiby employing such a compound.

(9) A marine antifouling agent containing a compound of the aboveformula (I) of (II), or its salt, as an active ingredient, or a methodfor controlling marine fouling organisms by employing such a compound.

Now, the present invention will be described in further detail withreference to Examples. However, it should be understood that the presentinvention is by no means restricted to such specific Examples. Firstly,Examples for preparing compounds of the present invention will bedescribed.

PREPARATION EXAMPLE 1

Preparation ofβ-(2-chlorophenyl)-β-isopropylcarbonyloxy-α-(2-thienyl)acrylonitrile(after-mentioned Compound No. b-35)

1) 1.12 g of sodium was added to 25 ml of dry ethanol, followed byheating to a reflux temperature. Then, a mixture comprising 5.0 g of2-thiopheneacetonitrile, 7.49 g of ethyl 2-chlorobenzoate and 25 ml ofdry ethanol, was dropwise added. After completion of the dropwiseaddition, the mixture was reacted for 1 hour under reflux.

After completion of the reaction, the reaction mixture was cooled andput into water, and the aqueous layer washed with methylene chloride wasweakly acidified with hydrochloric acid and extracted with methylenechloride. The obtained extracted layer was dried over anhydrous sodiumsulfate and concentrated under reduced pressure to obtain 1.6 g ofβ-(2-chlorophenyl)-β-hydroxy-α-(2-thienyl)acrylonitrile having a meltingpoint of from 164 to 167° C. The NMR spectrum data of this compound wereas follows.

¹H-NMR δppm (Solvent: CDCl₃/400 MHz)

6.54(s,1H), 7.18(dd,1H), 7.38-7.60(m,5H), 7.57(dd,1H)

2) 46 mg of triethylamine was added to a mixture comprising 0.12 g ofβ-(2-chlorophenyl)-β-hydroxy-α-(2-thienyl)acrylonitrile and 5 ml ofdichloroethane, followed by cooling with ice. Then, a mixture comprising54 mg of isobutylyl chloride and 2 ml of dichloroethane, was dropwiseadded. After completion of the dropwise addition, the mixture wasreturned to room temperature and reacted for 1.5 hours.

After completion of the reaction, the reaction mixture was put intowater and extracted with methylene chloride. The extracted layer waswashed with water, dried over anhydrous sodium sulfate and thenconcentrated under reduced pressure. The obtained residue was purifiedby silica gel column chromatography (developing solvent: ethylacetate/n-hexane=1/4) to obtain 0.12 g of the desired product having amelting point of from 84 to 86° C. The NMR spectrum data of this productwere as follows.

¹H-NMR δppm (Solvent: CDCl₃/400 MHz) 1.27(d,6H), 2.90(m,1H),7.11(dd,1H), 7.33-7.40(m,2H), 7.45(d,2H), 7.52(d,1H), 7.65(dd,1H)

PREPARATION EXAMPLE 2

Preparation ofα-(2,4-dichlorophenyl)-β-ethylsulfonyloxy-β-(2-trifluoromethylphenyl)acrylonitrile(after-mentioned Compound No. a-63)

1) A mixture comprising 3.7 g of 2-trifluoromethylbenzoyl chloride and15 ml of toluene, were dropwise added with stirring at room temperatureto a mixture comprising 3.0 g of 2,4-dichlorophenylacetonitrile, 45 mlof toluene, 1.63 g of triethylamine and 0.1 g of4-dimethylaminopyridine. After completion of the dropwise addition, themixture was reacted for 2 hours under reflux.

After completion of the reaction, the reaction mixture was cooled, putinto water and extracted with methylene chloride. The obtained extractedlayer was washed with water, dried over anhydrous sodium sulfate andthen concentrated under reduced pressure to obtain 6.13 g ofα-(2,4-dichlorophenyl)-β-(2-trifluoromethylphenyl)-β-(2-trifluoromethylbenzoyloxy)acrylonitrile.The NMR spectrum data of this compound were as follows.

¹H-NMR δppm (Solvent: CDCl₃/400 MHz) 7.21-7.45(m,3H), 7.49-7.88(m,8H)

2) 6.13 g ofα-(2,4-dichlorophenyl)-β-(2-trifluoromethylphenyl)-β-(2-trifluoromethylbenzoyloxy)acrylonitrileobtained in the above step, was, without purification, dissolved in 90ml of ethanol. A mixture comprising 0.69 g of sodium hydroxide and 12 mlof water, was added thereto, and the mixture was reacted at roomtemperature for 2.5 hours.

After completion of the reaction, the reaction mixture was put intowater, and the aqueous layer washed with methylene chloride was weaklyacidified with hydrochloric acid and extracted with methylene chloride.The obtained extracted layer was washed with water, dried over anhydroussodium sulfate and then concentrated under reduced pressure to obtain2.5 g ofα-(2,4-dichlorophenyl)-β-hydroxy-β-(2-trifluoromethylphenyl)acrylonitrile(after-mentioned Intermediate No. II-4) having a melting point of from182 to 183° C. The NMR spectrum data of this compound were as follows.

¹H-NMR δppm (Solvent: CDCl₃/400 MHz) 5.81(s,1H), 7.38-7.48(m,2H),7.54-7.65(m,1H), 7.66-7.82(m,4H)

3) 0.118 g of ethanesulfonyl chloride was added under cooling with iceto a mixture comprising 0.30 g ofα-(2,4-dichlorophenyl)-β-hydroxy-β-(2-trifluoromethylphenyl)acrylonitrile,7 ml of dichloroethane and 93 mg of triethylamine. Then, the mixture wasreturned to room temperature and reacted for 15 hours.

After completion of the reaction, the reaction mixture was washed withwater, dried over anhydrous sodium sulfate and then concentrated underreduced pressure. The obtained residue was purified by silica gel columnchromatography (developing solvent: ethyl acetate/n-hexane=1/4) toobtain 0.21 g of the desired product having a melting point of from 114to 116° C. The NMR spectrum data of this product were as follows.

¹H-NMR δppm (Solvent: CDCl₃/400 MHz) 1.14(t,3H), 2.75-2.94(m,2H),7.40(dd,1H), 7.47(d,1H), 7.57(d,1H), 7.71-7.78(m,2H), 7.85-7.89(m,2H)

PREPARATION EXAMPLE 3

Preparation ofα-(2,4-dichlorophenyl)-β-methylsulfonyloxy-β-(2-trifluoromethylphenyl)-acrylonitrile(after-mentioned Compound No. a-55)

93 mg of triethylamine was added to a mixture comprising 0.30 g ofα-(2,4-dichlorophenyl)-β-hydroxy-β-(2-trifluoromethylphenyl)acrylonitrileand 7 ml of dichloroethane. Then, 96 mg of methanesulfonyl chloride wasadded thereto, and the mixture was reacted for 17 hours at roomtemperature.

After completion of the reaction, the reaction mixture was washed withwater, dried over anhydrous sodium sulfate and then concentrated underreduced pressure. The obtained residue was purified by silica gel columnchromatography (developing solvent: ethyl acetate/n-hexane=1/6) toobtain 0.13 g of the desired oily product. The NMR spectrum data of thisproduct were as follows.

¹H-NMR δppm (Solvent: CDCl₃/400 MHz) 2.68(s,3H), 7.38(d,1H), 7.46(d,1H),7.54(s,1H), 7.70-7.77(m,2H), 7.84-7.89(m,2H)

PREPARATION EXAMPLE 4

Preparation ofα-(2,4-dichlorophenyl)-β-(n-propylsulfonyloxy)-β-(2-trifluoromethylphenyl)-acrylonitrile(after-mentioned Compound No. a-67)

Process 1

93 mg of triethylamine was added to a mixture comprising 0.30 g ofα-(2,4-dichlorophenyl)-β-hydroxy-β-(2-trifluoromethylphenyl)acrylonitrileand 7 ml of dichloroethane. Then, 0.13 g of n-propanesulfonyl chloridewas added thereto, and the mixture was reacted for 15 hours at roomtemperature.

After completion of the reaction, the reaction mixture was washed withwater, dried over anhydrous sodium sulfate and then concentrated underreduced pressure. The obtained residue was purified by silica gel columnchromatography (developing solvent: ethyl acetate/n-hexane=1/4) toobtain 0.15 g of the desired oily product. The NMR spectrum data of thisproduct were as follows.

¹H-NMR δppm (Solvent: CDCl₃/400 MHz) 0.87(t,3H), 1.52-1.64(m,2H),2.65-2.73(m,1H), 2.79-2.86(m,1H), 7.40(dd,1H), 7.47(d,1H), 7.57(d,1H),7.71-7.78(m,2H), 7.85-7.89(m,2H)

PREPARATION EXAMPLE 5

Preparation ofα-(2,4-dichlorophenyl)-β-(n-propylsulfonyloxy)-β-(2-trifluoromethylphenyl)-acrylonitrile(after-mentioned Compound No. a-67)

Process 2

2.22 g of triethylamine was added to a mixture comprising 5.60 g ofα-(2,4-dichlorophenyl)-β-hydroxy-β-(2-trifluoromethylphenyl)acrylonitrileand 50 ml of dichloroethane. Then, a mixture comprising 2.90 g ofn-propanesulfonyl chloride and 10 ml of dichloroethane, was dropwiseadded thereto. After completion of the dropwise addition, the mixturewas reacted for 2 hours at room temperature.

After completion of the reaction, the reaction mixture was washed withwater, dried over anhydrous sodium sulfate and then concentrated underreduced pressure. The obtained residue was purified by silica gel columnchromatography (developing solvent: ethyl acetate/n-hexane=1/6) toobtain 2.8 g of the desired product having a melting point of from 95 to96° C.

PREPARATION EXAMPLE 6

Preparation ofα-(4-chlorophenyl)-β-(n-butylsulfonyloxy)-β-(2-trifluoromethylphenyl)acrylonitrile(after-mentioned Compound No. a-156)

1) A mixture comprising 6.19 g of 2-trifluoromethylbenzoyl chloride and15 ml of toluene, was dropwise added with stirring at room temperatureto a mixture comprising 3.0 g of 4-chlorophenylacetonitrile, 30 ml oftoluene, 3.0 g of triethylamine and 0.1 g of 4-dimethylaminopyridine.After completion of the dropwise addition, the mixture was reacted for 8hours under reflux.

After completion of the reaction, the reaction mixture was cooled, putinto water and extracted with methylene chloride. The obtained extractedlayer was washed with water, dried over anhydrous sodium sulfate andthen concentrated under reduced pressure to obtain 3.08 g ofα-(4-chlorophenyl)-β-(2-trifluoromethylphenyl)-β-(2-trifluoromethylbenzoyloxy)acrylonitrile.

2) 3.08 g ofα-(4-chlorophenyl)-β-(2-trifluoromethylphenyl)-β-(2-trifluoromethylbenzoyloxy)acrylonitrileobtained in the above step was, without purification, dissolved in 40 mlof ethanol. A mixture comprising 0.50 g of sodium hydroxide and 10 ml ofwater was added thereto, and the mixture was reacted for 2 hours at roomtemperature.

After completion of the reaction, the reaction mixture was put intowater, and the aqueous layer washed with methylene chloride was weaklyacidified with hydrochloric acid and extracted with methylene chloride.The obtained extracted layer was washed with water, dried over anhydroussodium sulfate and then concentrated under reduced pressure to obtain1.68 g ofα-(4-chlorophenyl)-β-hydroxy-β-(2-trifluoromethylphenyl)acrylonitrile(after-mentioned Intermediate No. II-2) having a melting point of from146 to 148° C. The NMR spectrum data of this product were as follows.

¹H-NMR δppm (Solvent: CDCl₃/400 MHz) 7.41(d,2H), 7.58-7.68(m,5H),7.75(m,1H)

3) 86 mg of triethylamine was added to a mixture comprising 0.25 g ofα-(4-chlorophenyl)-β-hydroxy-β-(2-trifluoromethylphenyl)acrylonitrileand 8 ml of dichloroethane. Then, a mixture comprising 0.133 g ofn-butanesulfonyl chloride and 2 ml of dichloroethane, was dropwise addedthereto. After completion of the dropwise addition, the mixture wasreacted for 15 hours at room temperature.

After completion of the reaction, the reaction mixture was washed withwater, and the organic layer was dried over anhydrous sodium sulfate andthen concentrated under reduced pressure. The obtained residue waspurified by silica gel-column chromatography (developing solvent: ethylacetate/n-hexane=1/6) to obtain 0.12 g of the desired product having amelting point of from 63 to 64° C. The NMR spectrum data of this productwere as follows.

¹H-NMR δppm (Solvent: CDCl₃/400 MHz) 0.78(t,3H), 1.25(m,2H), 1.58(m,2H),2.78(m,2H), 7.45(d,2H), 7.63(d,2H), 7.72(m,2H), 7.82(m,2H)

PREPARATION EXAMPLE 7

Preparation ofα-(4-bromophenyl)-β-(ethylsulfonyloxy)-β-(2-trifluoromethylphenyl)acrylonitrile(after-mentioned Compound No. a-21)

1) A mixture comprising 17.55 g of 2-trifluoromethylbenzoyl chloride and30 ml of toluene, was dropwise added with stirring at room temperatureto a mixture comprising 15.0 g of 4-bromophenylacetonitrile, 120 ml oftoluene, 8.52 g of triethylamine and 0.5 g of 4-dimethylaminopyridine.After completion of the dropwise addition, the mixture was reacted for 4hours under reflux.

After completion of the reaction, the reaction mixture was cooled, putinto water and extracted with methylene chloride. The obtained extractedlayer was washed with water, dried over anhydrous sodium sulfate andthen concentrated under reduced pressure to obtain 21.25 g ofα-(4-bromophenyl)-β-(2-trifluoromethylphenyl)-β-(2-trifluoromethylbenzoyloxy)acrylonitrile.

2) 21.25 g ofα-(4-bromophenyl)-β-(2-trifluoromethylphenyl)-β-(2-trifluoromethylbenzoyloxy)acrylonitrileobtained in the above step was, without purification, dissolved in 60 mlof ethanol. Then, a mixture comprising 2.36 g of sodium hydroxide and 15ml of water, was added thereto, and the mixture was reacted for 2 hoursat room temperature.

After completion of the reaction, the reaction mixture was put intowater, and the aqueous layer washed with methylene chloride was weaklyacidified with hydrochloric acid and extracted with methylene chloride.The obtained extracted layer was washed with water, dried over anhydroussodium sulfate and then concentrated under reduced pressure to obtain9.52 g ofα-(4-bromophenyl)-β-hydroxy-β-(2-trifluoromethylphenyl)acrylonitrile(after-mentioned Intermediate No. II-3) having a melting point of from168 to 173° C.

3) 91 mg of triethylamine was added to a mixture comprising 0.30 g ofα-(4-bromophenyl)-β-hydroxy-β-(2-trifluoromethylphenyl)acrylonitrile and8 ml of dichloroethane. Then, a mixture comprising 0.11 g ofethanesulfonyl chloride and 2 ml of dichloroethane, was dropwise addedthereto. After completion of the dropwise addition, the mixture wasreacted for 15 hours at room temperature.

After completion of the reaction, the reaction mixture was washed withwater, and the organic layer was dried over anhydrous sodium sulfate andthen concentrated under reduced pressure. The obtained residue waspurified by silica gel column chromatography (developing solvent: ethylacetate/n-hexane=1/4) to obtain 0.14 g of the desired product having amelting point of from 131 to 132° C. The NMR spectrum data of thisproduct were as follows.

¹H-NMR δppm (Solvent: CDCl₃/400 MHz) 1.23(t,3H), 2.85(m,2H),7.56-7.62(m,4H), 7.71(m,2H), 7.83(m,2H)

PREPARATION EXAMPLE 8

Preparation ofα-(4-bromophenyl)-β-(n-propylsulfonyloxy)-β-(2-trifluoromethylphenyl)acrylonitrile(after-mentioned Compound No. a-22)

60 mg of triethylamine was added to a mixture comprising 0.20 g ofα-(4-bromophenyl)-β-hydroxy-β-(2-trifluoromethylphenyl)acrylonitrile and6 ml of dichloroethane. Then, a mixture comprising 77 mg ofn-propanesulfonyl chloride and 2 ml of dichloroethane, was dropwiseadded thereto. After completion of the dropwise addition, the mixturewas reacted for 15 hours at room temperature.

After completion of the reaction, the reaction mixture was washed withwater, and the organic layer was dried over anhydrous sodium sulfate andthen concentrated under reduced pressure. The obtained residue waspurified by silica gel column chromatography (developing solvent: ethylacetate/n-hexane=1/9) to obtain 0.10 g of the desired oily product. TheNMR spectrum data of this product were as follows.

¹H-NMR δppm (Solvent: CDCl₃/400 MHz) 0.86(t,3H), 1.65(m,2H), 2.76(m,2H),7.56-7.63(m,4H), 7.71(m,2H), 7.81(m,2H)

PREPARATION EXAMPLE 9

Preparation ofα-(4-bromophenyl)-β-(n-butylsulfonyloxy)-β-(2-trifluoromethylphenyl)acrylonitrile(after-mentioned Compound No. a-23)

60 mg of triethylamine was added to a mixture comprising 0.20 g ofα-(4-bromophenyl)-β-hydroxy-β-(2-trifluoromethylphenyl)acrylonitrile and6 ml of dichloroethane. Then, a mixture comprising 85 mg ofn-butanesulfonyl chloride and 2 ml of dichloroethane, was dropwise addedthereto. After completion of the dropwise addition, the mixture wasreacted for 15 hours at room temperature.

After completion of the reaction, the reaction mixture was washed withwater, and the organic layer was dried over anhydrous sodium sulfate andthen concentrated under reduced pressure. The obtained residue waspurified by silica gel column chromatography (developing solvent: ethylacetate/n-hexane=1/9) to obtain 70 mg of the desired oily product. TheNMR spectrum data of this product were as follows.

¹H-NMR δppm (Solvent: CDCl₃/400 MHz) 0.78(t,3H), 1.23(m,2H), 1.59(m,2H),2.78(m,2H), 7.57-7.63(m,4H), 7.71(m,2H), 7.82(m,2H)

PREPARATION EXAMPLE 10

Preparation ofα-(4-chlorophenyl)-β-(dimethylthiocarbamoyloxy)-β-(2-trifluoromethylphenyl)-acrylonitrile(after-mentioned Compound No. a-316)

A mixed solution comprising 0.42 g of dimethylthiocarbamoyl chloride and5 ml of acetonitrile, was dropwise added at room temperature to a mixedsolution comprising 1.0 g ofα-(4-chlorophenyl)-β-hydroxy-β-(2-trifluoromethylphenyl)acrylonitrile,0.47 g of triethylamine, a catalytic amount of 4-dimethylaminopyridineand 20 ml of acetonitrile. After completion of the dropwise addition,the mixture was reacted for 2 hours at 50° C.

After completion of the reaction, acetonitrile was distilled off underreduced pressure. Ethyl acetate and water were added to the residue tocarry out extraction. The organic layer was washed with water and asaturated sodium chloride aqueous solution and dried over anhydrousmagnesium sulfate. Then, the solvent was distilled off, and the residuewas purified by silica gel column chromatography (developing solvent:ethyl acetate/n-hexane=1/4) to obtain 0.82 g of the desired producthaving a melting point of 137.9° C. The NMR spectrum data of thisproduct were as follows.

¹H-NMR δppm (Solvent: CDCl₃/400 MHz) 3.10(s,3H), 3.22(s,3H),7.35-8.15(m,8H)

PREPARATION EXAMPLE 11

Preparation ofα-(4-chlorophenyl)-β-(S-ethyldithiocarbonyloxy)-β-(2-trifluoromethylphenyl)-acrylonitrile(after-mentioned Compound No. a-306)

A mixed solution comprising 500 mg ofα-(4-chlorophenyl)-β-hydroxy-β-(2-trifluoromethylphenyl)acrylonitrileand 2 ml of N,N-dimethylformamide were dropwise added under cooling withice to a mixture comprising 68 mg of 60% sodium hydride and 10 ml ofN,N-dimethylformamide. After completion of the dropwise addition, themixture was gradually returned to room temperature, and stirring wascontinued until generation of hydrogen gas completed. Then, the mixturewas again cooled with ice, and a mixed solution comprising 240 mg ofethyl chlorodithiocarbonate and 2 ml of N,N-dimethylformamide, wasdropwise added. After completion of the dropwise addition, the mixturewas reacted for 2 hours at room temperature.

After completion of the reaction, the reaction mixture was poured into100 ml of ice water and then extracted with 150 ml of ethyl ether. Theorganic layer was washed with water and a saturated sodium chlorideaqueous solution and dried over anhydrous magnesium sulfate. Then, thesolvent was distilled off, and the residue was purified by silica gelcolumn chromatography (developing solvent: ethyl acetate/n-hexane=1/9)to obtain 380 mg of the desired product having a refractive index n_(D)^(27.2) of 1.5612. The NMR spectrum data of this product were asfollows.

¹H-NMR δppm (Solvent: CDCl₃/400 MHz) 1.29(t,3H,J=7.80 Hz),3.08(q,2H,J=7.80 Hz), 7.01-7.93(m,8H)

PREPARATION EXAMPLE 12

Preparation ofα-(4-chlorophenyl)-β-(diethylaminosulfonyloxy)-β-(2-trifluoromethylphenyl)-acrylonitrile(after-mentioned Compound No. a-286)

0.18 g of triethylamine was added to a mixture comprising 0.3 g ofα-(4-chlorophenyl)-β-hydroxy-β-(2-trifluoromethylphenyl)acrylonitrileand 5 ml of dichloroethane. Then, 0.27 g of diethylsulfamoyl chloridewas added thereto, and the mixture was reacted for 3 hours under reflux.

After completion of the reaction, water was put into the reactionmixture and extracted with methylene chloride. The extracted organiclayer was washed with water and dried over anhydrous sodium sulfate.Then, it was concentrated under reduced pressure, and the obtainedresidue was purified by silica gel column chromatography (developingsolvent: ethyl acetate/n-hexane=15/85) to obtain 78 mg of the desiredoily product. The NMR spectrum data of this product were as follows.

¹H-NMR δppm (Solvent: CDCl₃/400 MHz) 1.05(t,6H), 3.06(m,4H), 7.42(d,2H),7.57(d,2H), 7.63-7.80(m,4H)

PREPARATION EXAMPLE 13

Preparation ofα-(4-chlorophenyl)-β-(S-methyldithiocarbonyloxy)-β-(2-trifluoromethylphenyl)-acrylonitrile(after-mentioned Compound No. a-305)

A mixed solution comprising 800 mg ofα-(4-chlorophenyl)-β-hydroxy-β-(2-trifluoromethylphenyl)acrylonitrileand 2 ml of N,N-dimethylformamide were dropwise added under cooling withice to a mixture comprising 110 mg of 60% sodium hydride and 10 ml ofN,N-dimethylformamide. After completion of the dropwise addition, themixture was gradually returned to room temperature, and the stirring wascontinued until generation of hydrogen gas completed. Then, the mixturewas cooled again with ice, and a mixed solution comprising 340 mg ofmethyl chlorodithiocarbonate and 2 ml of N,N-dimethylformamide, wasdropwise added thereto. After completion of the dropwise addition, themixture was reacted for 2 hours at room temperature.

After completion of the reaction, the reaction mixture was poured into100 ml of ice water. Then, 150 ml of ethyl ether was added thereto forextraction. The organic layer was washed with water and a saturatedsodium chloride aqueous solution and dried over anhydrous magnesiumsulfate. Then, the solvent was distilled off, and the residue waspurified by silica gel column chromatography (developing solvent: ethylacetate/n-hexane=1/9) to obtain 610 mg of the desired product having arefractive index n_(D) ^(39.4) of 1.5930. The NMR spectrum data of thisproduct were as follows.

¹H-NMR δppm (Solvent: CDCl₃/400 MHz) 2.47(s,3H), 2.53(s,3H),7.07-7.99(m,8H)

PREPARATION EXAMPLE 14

Preparation ofα-(4-chlorophenyl)-β-(dimethylaminosulfonyloxy)-β-(2-trifluoromethylphenyl)-acrylonitrile(after-mentioned Compound No. a-218)

1.25 g of triethylamine was added to a mixture comprising 2.0 g ofα-(4-chlorophenyl)-β-hydroxy-β-(2-trifluoromethylphenyl)acrylonitrileand 40 ml of dichloroethane. Then, 1.68 g of dimethylsulfamoyl chloridewas added thereto, and the mixture was reacted for 2 hours under reflux.

After completion of the reaction, water was added to the reactionmixture and extracted with methylene chloride. The extracted organiclayer was washed with water and dried over anhydrous sodium sulfate.Then, it was concentrated under reduced pressure, and the obtainedresidue was purified by silica gel column chromatography (developingsolvent: ethyl acetate/n-hexane=15/85) to obtain 2.50 g of the desiredproduct having a melting point of from 110 to 112° C. The NMR spectrumdata of this product were as follows.

¹H-NMR δppm (Solvent: CDCl₃/400 MHz) 2.66(s,6H), 7.43(d,2H), 7.60(d,2H),7.67-7.82(m,4H)

PREPARATION EXAMPLE 15

Preparation ofα-(4-chlorophenyl)-β-(ethyldithiooxy)-β-(2-trifluoromethylphenyl)acrylonitrile(after-mentioned Compound No. a-488)

1) 0.109 g of sulfur dichloride was added to a mixture comprising 0.25 gof α-(4-chlorophenyl)-β-hydroxy-β-(2-trifluoromethylphenyl)acrylonitrileand 10 ml of ethyl ether. Then, a mixture comprising 67 mg of pyridineand 10 ml of ethyl ether, was dropwise added thereto at −10° C., and themixture was returned to room temperature and reacted for 3 hours.

After completion of the reaction, the reaction mixture was filtered, andthe filtrate was concentrated under reduced pressure to obtain 0.30 g ofα-(4-chlorophenyl)-β-chlorosulfenyloxy-β-(2-trifluoromethylphenyl)acrylonitrile.

2) 0.30 g ofα-(4-chlorophenyl)-β-chlorosulfenyloxy-β-(2-trifluoromethylphenyl)acrylonitrileobtained in the above step was, without purification, dissolved in 10 mlof dichloroethane. Then, 58 mg of ethanethiol was added thereto, andthen 94 mg of triethylamine was added thereto under cooling with ice.The mixture was returned to room temperature and reacted for 1 hour.

After completion of the reaction, water was added to the reactionmixture and extracted with methylene chloride. The extracted organiclayer was washed with water, dried over anhydrous sodium sulfate andthen concentrated under reduced pressure. The obtained residue waspurified by silica gel column chromatography (developing solvent: ethylacetate/n-hexane=15/85) to obtain 0.20 g of the desired oily product.The NMR spectrum data of this product were as follows.

¹H-NMR δppm (Solvent: CDCl₃/400 MHz) 1.24(t,3H), 2.62-2.79(m,2H),7.12(d,1H), 7.43(d,2H), 7.49(t,1H), 7.60(d,2H), 7.74(d,1H)

Now, typical examples of the compound of the present invention of theabove formula (I) will be shown in Tables 1-a, 1-b, 1-c and 1-d, andtypical examples of the intermediate compound of the formula (II) willbe shown in Table 2. These compounds can be synthesized in accordancewith the above-described Preparation Examples or the above-describedvarious methods for producing the compound of the present invention orits intermediate compound.

TABLE I-a (Ia)

Comp. No.

R₁

Physical Property (Melting point) a-1

—SO₂CH₂CH₃

74˜75° C. a-2

—SO₂N(CH₃)₂

102˜104° C. a-3

—COCH₃

98˜100° C. a-4

—COCH₃

Oily a-5

—CO(CH₂)₂CH₃

Oily a-6

—CO(CH₂)₂CH₃

Oily a-7

—COCH(CH₃)₂

Oily a-8

—COC(CH₃)₃

83˜84° C. a-9

—COC(CH₃)₃

Oily a-10

—CO(CH₂)₂CH₃

Oily a-11

—COC(CH₃)₃

87˜92° C. a-12

—SO₂CH₃

104˜108° C. a-13

—SO₂CH₂CH₃

109˜112° C. a-14

—SO₂(CH₂)₂CH₃

86˜89° C. a-15

—COCH₃

a-16

—COCH₂CH₃

a-17

—CO(CH₂)₂CH₃

a-18

—COCH(CH₃)₂

a-19

—COC(CH₃)₃

a-20

—SO₂CH₃

105˜12° C. a-21

—SO₂CH₂CH₃

131˜132° C. a-22

—SO₂(CH₂)₂CH₃

Oily a-23

—SO₂(CH₂)₃CH₃

Oily a-24

—COSCH₃

Oily a-25

—COSCH₂CH₃

Oily a-26

—CH₃

a-27

—CH₂CH₃

133˜135° C. a-28

—CH₂CF₃

a-29

—CH₂OCH₃

E-isomer 99˜103° C. a-30

—COCH₃

138˜140° C. a-31

—COCH₃

75˜78° C. a-32

—COCH₃

a-33

—COCH₃

a-34

—COCH₂CH₃

93˜94° C. a-35

—COCH₂CH₃

a-36

—COCH₂CH₃

a-37

—COCH₂CH₃

a-38

—CO(CH₂)₂CH₃

59˜60° C. a-39

—CO(CH₂)₂CH₃

Oily a-40

—CO(CH₂)₂CH₃

a-41

—CO(CH₂)₂CH₃

a-42

—COCH(CH₃)₂

92˜94° C. a-43

—COCH(CH₃)₂

Oily a-44

—COCH(CH₃)₂

a-45

—COCH(CH₃)₂

a-46

—CO(CH₂)₃CH₃

Oily a-47

—COC(CH₃)₃

Oily a-48

—COC(CH₃)₃

Oily a-49

—COC(CH₃)₃

a-50

—COC(CH₃)₃

a-51

—CO(CH₂)₂Cl

a-52

—CO(CH₂)₂Cl

a-53

—SO₂CH₃

Z-isomer 121˜123° C. a-54

—SO₂CH₃

E-isomer 115˜117° C. a-55

—SO₂CH₃

Oily a-56

—SO₂CH₃

a-57

—SO₂CH₃

Amorphous a-58

—SO₂CH₃

a-59

—SO₂CH₃

a-60

—SO₂CH₃

a-61

—SO₂CH₃

a-62

—SO₂CH₂CH₃

a-63

—SO₂CH₂CH₃

E-isomer 114˜116° C. a-64

—SO₂CH₂CH₃

a-65

—SO₂CH₂CH₃

a-66

—SO₂(CH₂)₂CH₃

a-67

—SO₂(CH₂)₂CH₃

E-isomer 95˜96° C. a-68

—SO₂(CH₂)₂CH₃

a-69

—SO₂(CH₂)₂CH₃

a-70

—SO₂CH(CH₃)₂

109˜112° C. a-71

—SO₂(CH₂)₃CH₃

a-72

—SO₂(CH₂)₃CH₃

Oily a-73

—SO₂(CH₂)₃CH₃

a-74

—SO₂(CH₂)₃CH₃

a-75

—SO₂(CH₂)₄CH₃

a-76

—SO₂(CH₂)₂Cl

a-77

—SO₂CF₃

Oily a-78

—SO₂CF₃

n_(D) ^(48.2) 1.5430 a-79

—SO₂CH₂CF₃

a-80

—SO₂CH═CH₂

117˜120° C. a-81

—SO₂CH₂CH═CH₂

a-82

165˜167° C. a-83

—SO₂CH₃

Oily a-84

—SO₂CH₃

a-85

—SO₂CH₃

a-86

—COCH₃

a-87

—COCH₃

a-88

—COCH₂CH₃

a-89

—COCH₂CH₃

a-90

—CO(CH₂)₂CH₃

a-91

—CO(CH₂)₂CH₃

a-92

—COCH(CH₃)₂

a-93

—COCH(CH₃)₂

a-94

—COC(CH₃)₃

a-95

—COC(CH₃)₃

a-96

—SO₂CH₃

121˜124° C. a-97

—SO₂CH₃

115˜125° C. a-98

—SO₂CH₂CH₃

a-99

—SO₂CH₂CH₃

68˜71° C. a-100

—SO₂(CH₂)₂CH₃

a-101

—SO₂(CH₂)₂CH₃

a-102

—SO₂(CH₂)₃CH₃

a-103

—SO₂(CH₂)₃CH₃

a-104

—COCH₃

a-105

—COCH₃

a-106

—COCH₂CH₃

a-107

—COCH₂CH₃

a-108

—CO(CH₂)₂CH₃

a-109

—CO(CH₂)₂CH₃

a-110

—COCH(CH₃)₂

a-111

—COCH(CH₃)₂

a-112

—COC(CH₃)₃

a-113

—COC(CH₃)₃

a-114

—SO₂CH₃

a-115

—SO₂CH₃

a-116

—SO₂CH₂CH₃

a-117

—SO₂CH₂CH₃

a-118

—SO₂(CH₂)₂CH₃

a-119

—SO₂(CH₂)₂CH₃

a-120

—SO₂(CH₂)₃CH₃

a-121

—SO₂(CH₂)₃CH₃

a-122

—SO₂CH₃

a-123

—COCH₃

92˜95° C. a-124

—COCH₂CH₃

a-125

—CO(CH₂)₂CH₃

a-126

—COCH(CH₃)₂

a-127

—COC(CH₃)₃

a-128

—SO₂CH₃

125˜128° C. a-129

—SO₂CH₂CH₃

a-130

—SO₂(CH₂)₂CH₃

a-131

—SO₂(CH₂)₃CH₃

a-132

—COCH₃

a-133

—COCH₂CH₃

a-134

—CO(CH₂)₂CH₃

a-135

—COCH(CH₃)₂

a-136

—COC(CH₃)₃

a-137

—SO₂CH₃

130˜133° C. a-138

—SO₂CH₂CH₃

a-139

—SO₂(CH₂)₂CH₃

a-140

—SO₂(CH₂)₃CH₃

a-141

—COCH₃

a-142

—COCH₂CH₃

a-143

—CO(CH₂)₂CH₃

a-144

—COCH(CH₃)₂

a-145

—COC(CH₃)₃

a-146

—SO₂CH₃

a-147

—SO₂CH₂CH₃

a-148

—SO₂(CH₂)₂CH₃

a-149

—SO₂(CH₂)₃CH₃

a-150

—COC(CH₃)₃

n_(D) ^(30.8) 1.5432 a-151

—SO₂CH₃

147.3° C. a-152

—COC(CH₃)₃

n_(D) ^(30.8) 1.5336 a-153

—COCH₃

Oily a-154

—SO₂N(CH₃)₂

a-155

a-156

—SO₂(CH₂)₃CH₃

63˜64° C. a-157

—CS₂C≡CH

a-158

—SO₂CH₃

90˜93° C. a-159

—SO₂CH₃

Oily a-160

—COCH₃

77˜80° C. a-161

—COCH₂CH₃

65˜69° C. a-162

—COCH(CH₃)₂

83˜84° C. a-163

—SO₂(CH₂)₄CH₃

Oily a-164

—SO₂CH═CH₂

73˜76° C. a-165

—SO₂CF₃

Oily a-166

—SO₂CH₂CF₃

102˜105° C. a-167

—SO₂(CH₂)₃Cl

Oily a-168

—SO₂CH₃

95˜100° C. a-169

—SO₂CH₃

121˜123° C. a-170

—SO₂CH₃

Oily a-171

—SO₂CH₃

n_(D) ^(23.8) 1.5991 a-172

—SO₂CH₃

101.9° C. a-173

—SO₂N(CH₃)CH₂CH₃

77˜79° C. a-174

—COCH₃

a-175

—SO₂CH₃

95˜98° C. a-176

—SO₂CH₂CH₃

99˜102° C. a-177

—SO₂(CH₂)₂CH₃

101˜102° C. a-178

—SO₂(CH₂)₃CH₃

83˜85° C. a-179

—COSCH₃

Oily a-180

—SO₂(CH₂)₄CH₃

Oily a-181

—COSCH₂CH₃

65˜68° C. a-182

—COCH₃

a-183

—SO₂CH₃

112˜113° C. a-184

—SO₂CH₂CH₃

126˜128° C. a-185

—SO₂(CH₂)₂CH₃

106˜107° C. a-186

—SO₂(CH₂)₃CH₃

73˜75° C. a-187

—SO₂(CH₂)₃Cl

Oily a-188

—SO₂(CH₂)₂CH₃

Z-isomer 75˜77° C. a-189

—SO₂CH₂CH₃

Z-isomer Oily a-190

—SO₂CH₃

96˜98° C. a-191

—SO₂CH₂CH₃

84.2° C. a-192

—SO₂N(CH₃)CH₂CH₃

a-193

—COCH₃

a-194

—SO₂CH₃

81˜84° C. a-195

—SO₂CH₂CH₃

122˜125° C. a-196

—SO₂(CH₂)₂CH₃

65˜66° C. a-197

—SO₂(CH₂)₃CH₃

Oily a-198

a-199

—COCH₃

a-200

—SO₂CH₂CH₃

103˜105° C. a-201

—SO₂(CH₂)₂CH₃

80˜82° C. a-202

—SO₂(CH₂)₃CH₃

50˜52° C. a-203

—SO₂CH₃

133˜136° C. a-204

—SO₂CH₃

88˜91° C. a-205

a-206

—SO₂CH₃

101˜103° C. a-207

—SO₂(CH₂)₂CH₃

68˜70° C. a-208

—SO₂CH₃

127˜130° C. a-209

—CH₂CH₃

105˜107° C. a-210

—CH₂CH₂Cl

71˜73° C. a-211

—CH₂OCH₃

68˜72° C. a-212

—CH₂OCH₂CH₃

Oily a-213

—CH₂CH₂OCH₃

a-214

—SO₂CH(CH₃)₂

82˜84° C. a-215

—SO₂CH₂CH(CH₃)₂

80˜83° C. a-216

a-217

—SO₂C(CH₃)₃

a-218

—SO₂N(CH₃)₂

110˜112° C. a-219

—SO₂N(CH₃)₂

84˜86° C. a-220

—SO₂N(CH₃)₂

120˜121° C. a-221

—SO₂N(CH₃)₂

126˜127° C. a-222

—CH₂CH₂Cl

88˜90° C. a-223

—CH₂OCH₂CH₃

E-isomer 86˜88° C. a-224

—CH₂OCH₂CH₃

Z-isomer 77˜80° C. a-225

—CH₂CH₂OCH₃

111˜113° C. a-226

—CH₂SCH₃

E-isomer 87˜92° C. a-227

—SO₂CH₂CH(CH₃)₂

Oily a-228

a-229

—SO₂C(CH₃)₃

a-230

—SO₂N(CH₃)₂

137˜141° C. a-231

—SO₂(CH₂)₂CH₃

113.1° C. a-232

—SO₂CH₃

95.3° C. a-233

—SO₂CH₂CH₃

Oily a-234

—CH₃

100˜101° C. a-235

-(CH₂)₂CH₃

Oily a-236

—CH(CH₃)₂

81˜82° C. a-237

-(CH₂)₃CH₃

Oily a-238

—CH₂CH₂F

Oily a-239

—CH₂CF₃

Oily a-240

—CH₂CH═CH₂

Oily a-241

—CH₂C(Cl)═CH₂

a-242

—CH₂C(Cl)═CHCl

a-243

—CH₂C≡CH

a-244

—COCH₂OCH₃

Oily a-245

—COSCH₂CH₃

Oily a-246

—COCH₂CH═CH₂

a-247

—COCH₂C(Cl)═CH₂

a-248

—COCH₂C≡CH

a-249

—COCH₂C≡CCl

a-250

—CO₂CH₃

60˜63° C. a-251

—CO₂CH₂CH₃

Oily a-252

—CO₂CH₂CF₃

a-253

—CONH(CH₂)₂CH₃

a-254

—CON(CH₃)₂

58˜61° C. a-255

135˜138° C. a-256

109˜111° C. a-257

Oily a-258

106˜109° C. a-259

a-260

123˜124° C. a-261

124˜127° C. a-262

110˜113° C. a-263

Oily a-264

a-265

a-266

a-267

85˜87° C. a-268

a-269

a-270

a-271

a-272

a-273

a-274

—SCH₃

Oily a-275

—SOCH₃

a-276

—SOCH₂CH₃

a-277

—SO₂CH₃

153.9° C. a-278

—SO₂CH₃

Oily a-279

—SO₂CH₂OCH₃

a-280

—SO₂CH₂C(Cl)═CH₂

a-281

—SO₂CH₂C≡CCl

a-282

—SO₂OCH₂CH₃

98˜101° C. a-283

—SO₂SCH₂CH₃

a-284

—SO₂NH(CH₂)₂CH₃

a-285

—SO₂NHC(CH₃)₃

a-286

—SO₂N(CH₂CH₃)₂

Oily a-287

—SO₂N(CH₂CH₃)₂

a-288

Oily a-289

a-290

151˜155° C. a-291

152˜156° C. a-292

a-293

a-294

a-295

a-296

a-297

a-298

164˜167° C. a-299

Oily a-300

80˜82° C. a-301

—CSCH₃

a-302

—CSCH₂CH₃

a-303

—CSOCH₃

Oily a-304

—CSOCH₂CH₃

Oily a-305

—CS₂CH₃

n_(D) ^(39.4) 1.5930 a-306

—CS₂CH₂CH₃

n_(D) ^(27.2) 1.5612 a-307

—CS₂CH(CH₃)₂

n_(D) ^(33.8) 1.5824 a-308

—CS₂(CH₂)₃CH₃

80.3° C. a-309

—CS₂CH₂CF₃

a-310

—CS₂CH₂CH═CH₂

n_(D) ^(26.8) 1.6040 a-311

—CS₂CH₂CH═CCl₂

a-312

—CS₂CH₂C≡CH

a-313

—CS₂CH₂C≡Cl

a-314

a-315

—CSNHC(CH₃)₃

a-316

—CSN(CH₃)₂

137.9° C. a-317

—CSN(CH₂CH₃)₂

121˜123° C. a-318

Oily a-319

Oily a-320

a-321

a-322

113.8° C. a-323

n_(D) ^(39.4) 1.6204 a-324

a-325

71.9° C. a-326

a-327

a-328

129.6° C. a-329

125.8° C. a-330

—CH₂CN

Oily a-331

114˜116° C. a-332

74˜75° C. a-333

Oily a-334

123˜127° C. a-335

93˜94° C. a-336

109˜111° C. a-337

90˜91° C. a-338

140˜141° C. a-339

136˜137° C. a-340

98˜100° C. a-341

125˜130° C. a-342

Oily a-343

a-344

105˜110° C. a-345

a-346

a-347

a-348

Oily a-349

a-350

a-351

—CH₂COCH₃

a-352

—CH₂SOCH₃

a-353

—CH₂Si(CH₃)₃

Oily a-354

—CH₂C≡Cl

a-355

a-356

—SOCH₃

a-357

—SO₂CH₂C≡CH

a-358

—SO₂N(CH₃)₂

a-359

—SO₂N(CH₂CH₃)₂

44˜45° C. a-360

58˜59° C. a-361

a-362

—CS₂CH₂CH₃

n_(D) ^(31.0) 1.5762 a-363

—CSN(CH₃)₂

98˜100° C. a-364

—CSN(CH₃)CH₂CH₃

a-365

127.9° C. a-366

a-367

101˜104° C. a-368

—CH₂CH₃

Oily a-369

a-370

a-371

—SO₂N(CH₂CH₃)₂

71˜73° C. a-372

65˜66° C. a-373

173˜176° C. a-374

—CSCH₂OCH₂CH₃

a-375

—CS₂CH₂CH₃

102.4° C. a-376

—CSN(CH₃)₂

124˜128° C. a-377

—CSN(CH₃)₂

a-378

a-379

a-380

a-381

136.2° C. a-382

Oily a-383

—COSCH₂CF₃

a-384

—SO₂N(CH₂CH₃)₂

Oily a-385

a-386

154˜155° C. a-387

—CS₂CH₃

130.2° C. a-388

—CSN(CH₃)₂

141˜144° C. a-389

a-390

—CH₂OCH₃

Z-isomer 68˜70° C. a-391

—CH₂SCH₃

Z-isomer 113˜118° C. a-392

—COCH₂OCH₃

Oily a-393

—COSCH₂CH═CH₂

a-394

—CO₂CH₃

Oily a-395

—CO₂CH₂CH₃

Oily a-396

a-397

a-398

Oily a-399

—SO₂(CH₂)₃CH₃

Z-isomer Oily a-400

—SO₂SCH₂CH═CH₂

a-401

—SO₂NH(CH₂)₂CH₃

a-402

—SO₂NHC(CH₃)₃

a-403

—SO₂N(CH₂CH₃)₂

124˜125° C. a-404

105˜107° C. a-405

a-406

a-407

120˜121° C. a-408

a-409

a-410

—CSCH₃

a-411

—CSCH₂CH₃

a-412

—CSOCH₃

a-413

—CSOCH₂CH₃

Oily a-414

—CS₂CH₃

n_(D) ^(39.6) 1.5998 a-415

—CS₂CH₂CH₃

a-416

—CSCH₂C(Cl)═CHCl

a-417

—CSN(CH₃)₂

97˜98° C. a-418

—CSN(CH₂CH₃)₂

Oily a-419

a-420

a-421

Oily a-422

—CH₂CO₂CH₃

77˜80° C. a-423

—CH₂SO₂CH₃

Z-isomer 161˜163° C. a-424

—CH₂SO₂CH₃

E-isomer 175˜178° C. a-425

—CS₂CH₃

n_(D) ^(26.8) 1.5680 a-426

—CSN(CH₃)₂

109.2° C. a-427

139.1° C. a-428

—SO₂CH₂CH(CH₃)₂

Oily a-429

—SO₂N(CH₃)₂

64˜68° C. a-430

—SO₂N(CH₂CH₃)₂

95˜98° C. a-431

—CSN(CH₃)₂

87˜90° C. a-432

—COSCH₂CH═CCl₂

a-433

—SO₂SCH₂CH═CCl₂

a-434

—SO₂N(CH₃)₂

78˜80° C. a-435

—CSN(CH₃)₂

105˜107° C. a-436

—COSCH₂C≡CH

a-437

—COSCH₂C≡Cl

a-438

—COCH₃

a-439

—SO₂CH₂CH₃

a-440

—SO₂CH₂CH₃

Oily a-441

—CS₂CH₂CH₃

a-442

—CSN(CH₃)₂

a-443

—COSCH₃

Oily a-444

a-445

Oily a-446

a-447

a-448

a-449

a-450

a-451

—CS₂(CH₂)₂CH₃

71.9° C. a-452

—CS₂CH₂CO₂CH₃

n_(D) ^(26.6) 1.5825 a-453

—CS₂CH₂CO₂CH₂CH₃

a-454

—CS₂CH₃

a-455

—CS₂CH₂CO₂CH₃

a-456

100˜101° C. a-457

—CS₂CH₃

a-458

—CS₂CH₂CO₂CH₃

a-459

—SO₂N(CH₃)₂

115˜118° C. a-460

—SO₂N(CH₂CH₃)₂

Oily a-461

—CS₂CH₃

n_(D) ^(26.2) 1.5364 a-462

Oily a-463

72˜74° C. a-464

152˜155° C. a-465

110˜113° C. a-466

104˜106° C. a-467

99˜101° C. a-468

—COS(CH₂)₂CH₃

a-469

—CONHCH₃

Oily a-470

—SO₂N(CH₃)CH₂CH₃

98˜100° C. a-471

55˜57° C. a-472

Oily a-473

188˜191° C. a-474

—SCCl₃

Oily a-475

—SN(CH₃)₂

Oily a-476

—SN(CH₂CH₃)₂

a-477

a-478

—SCH₂CH₃

a-479

—S(CH₂)₂CH₃

a-480

—SCH(CH₃)₂

a-481

—SC(CH₃)₃

a-482

—SCH₂Cl

a-483

—SCHCl₂

a-484

—SCH₂OCH₃

a-485

—SCH₂SCH₃

a-486

—SCH₂N(CH₃)₂

a-487

—S₂CH₃

a-488

—S₂CH₂CH₃

Oily a-489

—S₂CH(CH₃)₂

a-490

—S₂C(CH₃)₃

a-491

—SN(CH₃)OCH₃

a-492

—SN(CH₂CH₃)OCH₃

a-493

a-494

a-495

a-496

a-497

a-498

—SO₂N(CH₃)OCH₃

a-499

a-500

—SO₂CH₂N(CH₃)₂

a-501

a-502

—SO₂(CH₂)₂OCH₃

a-503

—SO₂CH₂SCH₃

a-504

—SO₂(CH₂)₂SCH₃

a-505

a-506

a-507

a-508

a-509

a-510

a-511

a-512

a-513

a-514

a-515

a-516

a-517

a-518

—SON(CH₃)₂

a-519

—SON(CH₂CH₃)₂

a-520

—SON(CH₃)OCH₃

a-521

—SON(CH₂CH₃)OCH₃

a-522

—S(═O)OCH₃

a-523

—S(═O)OCH₂CH₃

a-524

—S(═O)SCH₃

a-525

—S(═O)SCH₂CH₃

a-526

118˜120° C. a-527

a-528

—COCH₂SOCH₃

a-529

—COCH₂SO₂CH₃

a-530

—CO(CH₂)₂NH₂

a-531

—COCH₂NHCH₃

a-532

—COCH₂N(CH₃)₂

a-533

a-534

a-535

123˜124° C. a-536

125˜128° C. a-537

28˜30° C. a-538

a-539

a-540

170˜175° C. a-541

a-542

—CSOCH(CH₃)₂

a-543

—CSOC(CH₃)₃

a-544

—CSOCH₂CF₃

a-545

—CSOCH₂CH═CH₂

a-546

—CSOCH₂C≡CH

a-547

—CSOCH₂CH═CCl₂

a-548

—CSOCH₂C≡Cl

a-549

a-550

a-551

a-552

a-553

a-554

a-555

a-556

a-557

a-558

a-559

a-560

a-561

a-562

a-563

a-564

—CH₂CSCH₃

a-565

—CH₂CSOCH₃

a-566

a-567

a-568

a-569

a-570

a-571

a-572

a-573

E-isomer 116.1° C. a-574

Z-isomer n_(D) ^(39.2) 1.5716 a-575

a-576

a-577

a-578

a-579

a-580

a-581

a-582

a-583

a-584

a-585

a-586

a-587

a-588

—CS₂(CH₂)₂SCH₃

a-589

a-590

—CS₂(CH₂)₂CN

a-591

—CS₂(CH₂)₂NO₂

a-592

—CS₂(CH₂)₂OCHF₂

a-593

—CS₂CCl₃

a-594

a-595

a-596

a-597

a-598

a-599

—COCH₃

a-600

—COCH₂CH₃

a-601

—COCH(CH₃)₂

a-602

—COC(CH₃)₃

a-603

—SO₂CH₃

a-604

—SO₂CH₂CH₃

a-605

—SO₂N(CH₃)₂

a-606

—SO₂N(CH₂CH₃)₂

a-607

a-608

—CO₂CH₃

a-609

—CO₂CH₂CH₃

a-610

a-611

—CSOCH₃

a-612

—CSOCH₂CH₃

a-613

a-614

—CSN(CH₃)₂

a-615

—CS₂CH₃

a-616

—CS₂CH₂CH₃

a-617

—CS₂CH₂CH═CH₂

a-618

—CSN(CH₃)₂

a-619

—CS₂CH₃

a-620

—CS₂CH₂CH₃

a-621

—CS₂CH₂CH═CH₂

a-622

—SO₂N(CH₃)₂

a-623

—SO₂N(CH₂CH₃)₂

a-624

a-625

—COCH₃

a-626

—COCH(CH₃)₂

a-627

—COC(CH₃)₃

a-628

—SO₂CH₃

a-629

—SO₂CH₂CH₃

a-630

—SO₂N(CH₃)₂

a-631

—SO₂N(CH₂CH₃)₂

a-632

a-633

—SO₂N(CH₃)₂

a-634

—SO₂N(CH₃)₂

a-635

—SO₂N(CH₃)₂

a-636

—SO₂N(CH₃)₂

a-637

—COSCH₃

Oily a-638

—COSCH₂CH₃

Oily a-639

107˜110° C. a-640

83˜84° C. a-641

110˜111° C. a-642

—COCH₃

a-643

—COCH₂CH₃

a-644

—COCH(CH₃)₂

a-645

—COC(CH₃)₃

a-646

—SO₂CH₃

a-647

—SO₂CH₂CH₃

a-648

—SO₂N(CH₃)₂

a-649

—SO₂N(CH₂CH₃)₂

a-650

a-651

a-652

—CO₂CH₃

a-653

—CO₂CH₂CH₃

a-654

a-655

a-656

—CSOCH₃

a-657

—CSOCH₂CH₃

a-658

a-659

—CSN(CH₃)₂

a-660

—CS₂CH₃

a-661

—CS₂CH₂CH₃

a-662

57˜58° C. a-663

119˜120° C. a-664

130˜132° C. a-665

—CS₂CH₃

n_(D) ^(30.2) 1.5922 a-666

—CS₂CH₃

E-isomer 79.2° C. a-667

—CS₂CH₃

Z-isomer n_(D) ^(18.6) 1.6004 a-668

—CS₂CH₃

n_(D) ^(38.8) 1.5062 a-669

—SO₂CH₃

a-670

—SO₂CH₂CH₃

a-671

—SO₂N(CH₃)₂

a-672

—SO₂N(CH₂CH₃)₂

a-673

a-674

—SCH₃

a-675

—SCH₂CH₃

a-676

—SCCl₃

a-677

a-678

—SN(CH₃)₂

a-679

—SN(CH₂CH₃)₂

a-680

—CSOCH₃

Oily a-681

—CSOCH₂CH₃

Oily a-682

Oily a-683

—COSCH₃

Oily a-684

—COSCH₂CH₃

116˜117° C. a-685

a-686

—CS₂CH₃

n_(D) ^(31.8) 1.5746 a-687

—SCH₃

a-688

—SCH₂CH₃

a-689

—SCCl₃

a-690

—SN(CH₃)₂

a-691

—SN(CH₂CH₃)₂

a-692

—CS₂CH₃

103.6° C. a-693

—CS₂CH₃

a-694

—CS₂CH₃

a-695

—CS₂CH₃

a-696

—CS₂CH₃

a-697

—CS₂CH₃

a-698

—CS₂CH₃

a-699

—CS₂CH₃

a-700

—CS₂CH₃

a-701

—CS₂CH₃

a-702

—CS₂CH₃

a-703

—CS₂CH₃

a-704

—CS₂CH₃

a-705

—CS₂CH₃

a-706

—CS₂CH₃

a-707

—CS₂CH₃

a-708

—CS₂CH₃

a-709

—CS₂CH₃

a-710

—CS₂CH₃

a-711

—CS₂CH₃

a-712

—CS₂CH₃

a-713

—CS₂CH₃

88.0° C.

TABLE I-b (Ib)

Comp. No.

R₁

Physical property (Melting point) b-1

—CSOCH₃

b-2

—CSOCH₂CH₃

b-3

b-4

—CSCH₃

b-5

—CSCH₂CH₃

b-6

—CSCH₂CH═CH₂

b-7

—CSCH₂C≡Cl

b-8

—CSOCH₃

b-9

—CSOCH₂CH₃

b-10

—CSOCH₂CH═CH₂

b-11

—CSOCH₂C≡Cl

b-12

—CS₂CH₃

n_(D) ^(38.2) 1.5888 b-13

—CS₂CH₂CH₃

106.2° C. b-14

—CS₂CH₂CH═CH₂

b-15

—CS₂CH₂C≡Cl

b-16

b-17

b-18

b-19

b-20

b-21

Oily b-22

b-23

b-24

b-25

b-26

b-27

b-28

b-29

b-30

b-31

b-32

b-33

b-34

b-35

b-36

—COSCH₃

b-37

—COSCH₂CH₃

b-38

—COSCH₂CH═CH₂

b-39

—COSCH₂C≡Cl

b-40

b-41

—CSOCH₃

b-42

—CSOCH₂CH₃

b-43

—CS₂CH₃

b-44

—CS₂CH₂CH₃

b-45

—CS₂CH₂CH═CH₂

b-46

b-47

—COSCH₃

b-48

—COSCH₂CH₃

b-49

—COSCH₂CH═CH₂

b-50

—COSCH₂C≡Cl

b-51

TABLE I-c (Ic)

Comp. No.

R₁

Physical property (Melting point) c-1

—COCH₃

120˜123° C. c-2

—COCH₃

c-3

—COCH₂CH₃

c-4

—CO(CH₂)₂CH₃

c-5

—COCH(CH₃)₂

c-6

—COC(CH₃)₃

93˜95° C. c-7

—COC(CH₃)₃

c-8

—CON(CH₃)₂

Oily c-9

—SO₂CH₃

c-10

—SO₂CH₂CH₃

c-11

—SO₂(CH₂)₂CH₃

c-12

—COCH₃

c-13

—COCH₃

101˜102° C. c-14

—COCH₃

c-15

—COCH₂CH₃

c-16

—CO(CH₂)₂CH₃

c-17

—COCH(CH₃)₂

c-18

—COC(CH₃)₃

139˜140° C. c-19

—COC(CH₃)₃

c-20

—SO₂CH₃

c-21

—SO₂CH₂CH₃

c-22

—SO₂(CH₂)₂CH₃

c-23

—SO₂CH₃

c-24

—COCH₃

c-25

—COCH₂CH₃

c-26

—CO(CH₂)₂CH₃

c-27

—COCH(CH₃)₂

c-28

—COC(CH₃)₃

c-29

—SO₂CH₃

c-30

—SO₂CH₂CH₃

c-31

—SO₂(CH₂)₂CH₃

c-32

—SO₂CH₂CH₃

c-33

—SO₂N(CH₃)₂

c-34

—COCH₃

72˜73° C. c-35

—COCH₂CH₃

c-36

—CO(CH₂)₂CH₃

c-37

—COCH(CH₃)₂

c-38

—COC(CH₃)₃

c-39

—SO₂CH₃

c-40

—SO₂CH₂CH₃

c-41

 SO₂(CH₂)₂CH₃

c-42

—SO₂N(CH₃)₂

121˜123° C. c-43

—SO₂N(CH₃)₂

205˜207° C. c-44

—COCH₃

198˜200° C. c-45

—COCH₂CH₃

c-46

—CO(CH₂)₂CH₃

c-47

—COCH(CH₃)₂

c-48

—COC(CH₃)₃

c-49

—SO₂CH₃

c-50

—SO₂CH₂CH₃

c-51

—SO₂(CH₂)₂CH₃

c-52

—COCH₃

c-53

—COCH₃

c-54

—COCH₂CH₃

c-55

—CO(CH₂)₂CH₃

c-56

—COCH(CH₃)₂

c-57

—COC(CH₃)₃

c-58

—SO₂CH₃

c-59

—SO₂CH₂CH₃

c-60

—SO₂(CH₂)₂CH₃

c-61

Z-isomer 116˜120° C. c-62

Oily c-63

E-isomer 171˜176° C. c-64

138˜142° C. c-65

—SO₂N(CH₂CH₃)₂

TABLE I-d (Id)

Comp. No.

R₁

Physical property (Melting point) d-1

—COCH₃

d-2

—CO₂CH₃

d-3

—CS₂CH₃

E-isomer n_(D) ^(39.2) 1.5352 d-4

—CS₂CH₃

Z-isomer n_(D) ^(39.2) 1.5651 d-5

—CS₂CH₂CH₃

d-6

—SO₂N(CH₃)₂

d-7

—SO₂N(CH₂CH₃)₂

d-8

—COCH₃

d-9

—CO₂CH₃

d-10

—CS₂CH₃

d-11

—CS₂CH₂CH₃

d-12

—SO₂N(CH₃)₂

d-13

—SO₂N(CH₂CH₃)₂

d-14

—COCH₃

d-15

—CO₂CH₃

d-16

—CS₂CH₃

d-17

—CS₂CH₂CH₃

d-18

—SO₂N(CH₃)₂

d-19

—SO₂N(CH₂CH₃)₂

d-20

—COCH₃

d-21

—CO₂CH₃

d-22

—CS₂CH₃

d-23

—CS₂CH₂CH₃

d-24

—SO₂N(CH₃)₂

d-25

—SO₂N(CH₂CH₃)₂

d-26

—COCH₃

d-27

—CO₂CH₃

d-28

—CS₂CH₃

d-29

—CS₂CH₂CH₃

d-30

—SO₂N(CH₃)₂

d-31

—SO₂N(CH₂CH₃)₂

d-32

—COCH₃

d-33

—CO₂CH₃

d-34

—CS₂CH₃

d-35

—CS₂CH₂CH₃

d-36

—SO₂N(CH₃)₂

d-37

—SO₂N(CH₂CH₃)₂

TABLE 2 (II)

Inter- mediate No. Q

Physical property (Melting point) II-1

154˜156° C. II-2

146˜148° C. II-3

168˜173° C. II-4

182˜183° C. II-5

II-6

120˜130° C. II-7

II-8

164˜167° C. II-9

II-10

II-11

145˜150° C. II-12

175˜177° C. II-13

II-14

II-15

II-16

II-17

187˜189° C. II-18

118˜121° C. II-19

139˜144° C. II-20

170˜180° C. II-21

188˜189° C. II-22

176˜180° C. II-23

87˜90° C. II-24

II-25

156˜158° C. II-26

90˜92° C. II-27

II-28

II-29

II-30

II-31

II-32

II-33

II-34

II-35

II-36

II-37

II-38

II-39

II-40

II-41

II-42

II-43

II-44

II-45

II-46

II-47

II-48

II-49

II-50

II-51

II-52

II-53

II-54

II-55

II-56

II-57

II-58

II-59

II-60

II-61

II-62

II-63

II-64

II-65

II-66

II-67

II-68

II-69

105˜108° C. II-70

II-71

II-72

II-73

II-74

II-75

II-76

II-77

II-78

II-79

II-80

II-81

II-82

115˜119° C. II-83

206˜213° C. II-84

II-85

II-86

II-87

II-88

II-89

II-90

II-91

Now, Test Examples will be described.

TEST EXAMPLE 1

Miticidal test against adults of two-spotted spider mite (Tetranychusurticae)

A miticidal solution was prepared to bring the concentration of acompound of the present invention to 800 ppm. Kidney bean (Phaseolusvulgaris) seedling with only one primary leaf left, was transplanted ina cup (diameter: 8 cm, height: 7 cm) and 30 adults of two-spotted spidermite (Tetranychus urticae) were inoculated thereto. The adult mites wereimmersed together with the kidney bean leaf in the above miticidalsolution for about 10 seconds, then dried in air and left in a constanttemperature chamber at 26° C. with lightening. On the second day afterthe treatment, dead adult mites were counted, and the mortality wascalculated by the following equation.${{Mortality}\quad (\%)} = {\frac{{Number}\quad {of}\quad {dead}\quad {adult}\quad {mites}}{{Number}\quad {of}\quad {treated}\quad {adult}\quad {mites}} \times 100}$

As a result, the mortality was at least 90% with each of Compound Nos.a-6 to 7, a-10 to 14, a-20 to 25, a-29, a-31, a-39, a-43, a-46 to 48,a-55, a-63, a-67, a-72, a-77 to 78, a-80, a-83, a-97, a-99, a-153,a-156, a-160 to 164, a-166 to 167, a-173, a-175 to 181, a-183 to 189,a-191, a-194 to 197, a-200 to 202, a-206 to 207, a-209, a-211 to 212,a-214 to 215, a-218 to 221, a-223 to 224, a-227, a-230, a-240, a-244,a-245, a-250 to 251, a-254 to 258, a-260 to 263, a-267, a-274, a-286,a-288, a-290, a-298, a-300, a-303 to 308, a-310, a-316 to 319, a-322,a-323, a-325, a-328 to 329, a-331, a-335, a-342, a-359, a-360, a-362 to363, a-365, a-367 to 368, a-371 to 373, a-375 to 376, a-381, a-382,a-384, a-386 to 388, a-390, a-392, a-394 to 395, a-398, a-403, a-413 to414, a-417 to 418, a-425 to 426, a-428 to 431, a-434 to 435, a-443,a-445, a-451 to 452, a-459 to 463, a-465 to 467, a-469 to 472, a-474,a-475, a-573, a-574, a-637 to 641, a-664 to 667, a-686, c-34, c-43 andc-44 and with intermediate No. II-2.

TEST EXAMPLE 2

Ovicidal test against two-spotted spider mite (Tetranychus urticae)

An ovicidal solution was prepared to bring the concentration of acompound of the present invention to 800 ppm. Kidney bean (Phaseolusvulgaris) seedling with only one primary leaf left,. was transplanted ina cup (diameter: 8 cm, height: 7 cm), and adults of two-spotted spidermite (Tetranychus urticae) were inoculated thereto and permitted to layeggs for 24 hours, whereupon the adult mites were removed. The eggs weredipped together with the kidney bean leaf in the above ovicidal solutionfor about 10 seconds, then dried in air and left in a constanttemperature chamber at 26° C. with lightening. On the 7th day after thetreatment, hatching of the eggs was investigated, and the ovicidal ratiowas obtained by the following equation.${{Ovicidal}\quad {ratio}\quad (\%)} = {\frac{{Number}\quad {of}\quad {dead}\quad {eggs}}{{Number}\quad {of}\quad {treated}\quad {eggs}} \times 100}$

As a result, the ovicidal ratio was at least 90% with each of CompoundNos. a-10 to 14, a-20 to 25, a-29, a-31, a-38 to 39, a-43, a-46 to 48,a-55, a-63, a-67, a-70, a-72, a-77 to 78, a-80, a-83, a-97, a-99, a-150,a-156, a-160 to 164, a-166 to 168, a-173, a-175 to 181, a-183 to 189,a-191, a-194 to 197, a-200 to 202, a-204, a-206 to 207, a-209, a-211 to212, a-214 to 215, a-218 to 221, a-223 to 224, a-227, a-230, a-233 to234, a-240, a-244, a-245, a-250 to 251, a-254 to 258, a-260 to 262,a-267, a-274, a-282, a-286, a-288, a-298, a-300, a-303 to 308, a-310,a-316 to 319, a-322, a-323, a-325, a-328 to 329, a-331 to 333, a-335,a-337, a-342, a-348, a-359, a-360, a-362 to 363, a-365, a-367 to 368,a-371 to 372, a-375 to 376, a-381, a-382, a-384, a-386 to 388, a-390,a-394 to 395, a-399, a-403, a-407, a-413 to 414, a-417 to 418, a-425 to426, a-428 to 431, a-434 to 435, a-443, a-445, a-451, a-452, a-456,a-459 to 463, a-465 to 467, a-470 to 472, a-474, a-475, a-573, a-574,a-637 to 641, a-662 to 667, a-686, c-34, c-43 and c-44.

TEST EXAMPLE 3

Insecticidal test against small brown planthopper (Laodelphaxstriatellus)

Rice seedling was dipped for about 10 seconds in an insecticidalsolution prepared to bring the concentration of a compound of thepresent invention to 800 ppm and then dried in air. Then, the seedlingwith its root wrapped with a wet absorbent cotton, was put into a testtube. Then, 10 larvae of small brown planthopper (Laodelphaxstriatellus) were released therein, and the test tube was covered with agauze and left in a constant chamber at 26° C. with lightening. On the5th day after the release, dead larvae were counted, and the mortalitywas calculated by the following equation.${{Mortality}\quad (\%)} = {\frac{{Number}\quad {of}\quad {dead}\quad {insects}}{{Number}\quad {of}\quad {released}\quad {insects}} \times 100}$

As a result, the mortality was at least 90% with each of Compound Nos.a-10 to 11, a-161, a-362, a-474, a-637, a-638 and c-34.

TEST EXAMPLE 4

Insecticidal test against green peach aphid (Myzus persicae)

An insecticidal solution was prepared to bring the concentration of acompound of the present invention to 800 pm. The petiole of each ofeggplants with only one foliage leaf left (planted in a pot having adiameter of 8 cm and a height of 7 cm) was coated with a sticker, andabout 2-3 apterous viviparous female of green peach aphid (Myzuspersicae) were infested and incubated on the foliage leaf of theeggplant. After two days from the infestation, the adult insects wereremoved, and the number of larvae was counted. Then, the foliage leaf ofthe eggplant infested with the larvae was dipped in the aboveinsecticidal solution for about 10 seconds, then dried in air and leftin a constant temperature chamber at 26° C. with lightening. On the 5thday after the treatment, dead insects were counted, and the mortalitywas calculated by the following equation:${{Mortality}\quad (\%)} = {\frac{{Number}\quad {of}\quad {dead}\quad {insects}}{{Number}\quad {of}\quad {treated}\quad {insects}} \times 100}$

The insects released from the leaf were counted as dead insects.

As a result, the mortality was at least 90% with each of Compound Nos.a-10 to 11, a-160 to 162, a-637 and a-638.

TEST EXAMPLE 5

Test on preventive effect against tomato late blight

Tomato (cultivar: Ponderosa) was cultivated in a polyethylene pot havinga diameter of 7.5 cm. When the tomato reached a four-leaf stage, it wassprayed with 10 ml of a solution having a predetermined concentration ofa compound of the present invention through a spray gun. After thesolution was dried, the tomato plant was sprayed and inoculated with azoosporangia suspension of fungi of late blight (Phytophthora infestans)and kept in a constant-temperature chamber at 20° C.

Third to fourth day after the inoculation, the area of lesions wasexamined, and the control index was determined according to thefollowing criteria for evaluation.

Degree of disease outbreak Control index (visual observation) 5 Nolesions are recognizable at all. 4 The area, number or length of lesionsis less than 10% of that in the non-treated plot. 3 The area, number orlength of lesions is less than 40% of that in the non-treated plot. 2The area, number or length of lesions is less than 70% of that in thenon-treated plot. 1 The area, number or length of lesions is 70% or moreof that in the non-treated plot.

As a result, Compound No. a-3 exhibited a control index of 5 at aconcentration of 250 ppm.

TEST EXAMPLE 6

Test on preventive effect against wheat powdery mildew

Wheat (cultivar: Norin No. 61) was cultivated in a polyethylene pothaving a diameter of 7.5 cm. When the wheat reached a 1.5 leaf stage, itwas sprayed with 10 ml of a solution having a predeterminedconcentration of a compound of the present invention through a spraygun. After the solution was dried, the wheat was dusted and inoculatedwith conidia of fungi of powdery mildew (Erysiphe graminis) and kept ina constant-temperature chamber at 20° C.

Eighth day after the inoculation, the area of lesions or thespore-formation area was examined, and the control index was determinedaccording to the following criteria for evaluation.

Degree of disease outbreak Control index (visual observation) 5 Nolesion or spore-formation is recognizable at all. 4 The area or numberof lesions or the spore-formation area is less than 10% of that in thenon-treated plot. 3 The area or number of lesions or the spore-formationarea is less than 40% of that in the non-treated plot. 2 The area ornumber of lesions or the spore-formation area is less than 70% of thatin the non-treated plot. 1 The area or number of lesions or thespore-formation area is 70% or more of that in the non-treated plot.

As a result, Compounds Nos. a-7, a-30, a-63, a-67, a-77 to 78, a-123 anda-234 exhibited a control index of 5 at a concentration of 500 pm, andCompounds Nos. a-3, a-38 to 39 and a-46 exhibited a control index of 5or 4 at a concentration of 250 ppm.

TEST EXAMPLE 7

Test on preventive effect against oat crown rust

Oat (cultivar: Zenshin) was cultivated in a polyethylene pot having adiameter of 7.5 cm. When the oat reached a 1.5 leaf stage, it wassprayed with 10 ml of a solution having a predetermined concentration ofa compound of the present invention through a spray gun.

After the solution was dried, the oat was sprayed and inoculated with aspore suspension of fungi of crown rust (Puccinia coronata). Eighth dayafter the inoculation, the area of lesions or spore-formation area wasexamined and the control index was determined in the same manner as inTest Example 6.

As a result, compound Nos. a-78, a-123 and a-166 exhibited a controlindex of 5 at a concentration of 500 ppm, and Compound No. a-3 exhibiteda control index of 5 at a concentration of 250 ppm.

TEST EXAMPLE 8

Control test against green algae

Green algae preliminarily cultured for 7 days ({circle around (1)}Selenastrum capricornutum or {circle around (2)}: Chlorella vulgaris)were inoculated to a culture medium for algae containing a solutionprepared to bring the concentration of a compound of the presentinvention to 100 ppm, and left to stand for 8 days in a constanttemperature chamber at 20° C. with lighting, whereupon growth degree ofthe green algae was investigated, and the control index was determinedaccording to the following criteria for evaluation.

Control index Growth degree (visual observation) A No growth of greenalgae is observed at all B Growth of green algae is slightly observed. CGrowth of green algae is observed in the same degree as in thenon-treated plot.

As a result, Compound Nos. a-3, a-6 and a-70 exhibited a control indexof A against green algae {circle around (1)} at a concentration of 100ppm. Further, against green algae {circle around (2)}, Compound Nos.a-3, a-6, a-26 and a-39 exhibited a control index of A at aconcentration of 100 ppm.

Now, formulation Examples will be described.

FORMULATION EXAMPLE 1

(a) Compound No. a-31 20 parts by weight (b) Clay 72 parts by weight (c)Sodium lignin sulfonate 8 parts by weight

The above components are uniformly mixed to obtain a wettable powder.

FORMULATION EXAMPLE 2

(a) Compound No. b-26 5 parts by weight (b) Talc 95 parts by weight

The above components are uniformly mixed to obtain a dust.

FORMULATION EXAMPLE 3

(a) Compound No. a-39 20 parts by weight (b) N,N′-dimethylacetamide 20parts by weight (c) Polyoxyethylenealkylphenyl 10 parts by weight ether(d) Xylene 50 parts by weight

The above components are uniformly mixed and dissolved to obtain anemulsifiable concentrate.

FORMULATION EXAMPLE 4

(a) Clay 68 parts by weight (b) Sodium lignin sulfonate 2 parts byweight (c) Polyoxyethylenealkylaryl 5 parts by weight sulfate (d) Finesilica powder 25 parts by weight

A mixture of the above components is mixed with compound No. b-31 in aweight ratio of 4:1 to obtain a wettable powder.

FORMULATION EXAMPLE 5

(a) Compound No. b-35 50 parts by weight (b) Oxylated polyalkylphenyl 2parts by weight phosphate-triethanolamine (c) Silicone 0.2 part byweight (d) Water 47.8 parts by weight

The above components are uniformly mixed and pulverized to obtain a baseliquid, and

(e) Sodium polycarboxylate 5 parts by weight (f) Anhydrous sodiumsulfate 42.8 parts by weight

are added, and the mixture is uniformly mixed and dried to obtainwater-dispersible granules.

FORMULATION EXAMPLE 6

(a) Compound No. b-48 5 parts by weight (b) Polyoxyethyleneoctylphenyl 1part by weight ether (c) Phosphoric acid ester of 0.1 part by weightpolyoxyethylene (d) Granular calcium carbonate 93.5 parts by weight

The above components (a) to (c) are preliminarily uniformly mixed anddiluted with a proper amount of acetone, and then the mixture is sprayedonto the component (d), and acetone is removed to obtain granules.

FORMULATION EXAMPLE 7

(a) Compound No. a-47 2.5 parts by weight (b) N-methyl-2-pyrrolidone 2.5parts by weight (c) Soybean oil 95.0 parts by weight

The above components are uniformly mixed and dissolved to obtain anultra low volume formulation.

FORMULATION EXAMPLE 8

(a) Compound No. a-55 5 parts by weight (b) N,N′-dimethylacetamide 15parts by weight (c) Polyoxyethylenealkylaryl 10 parts by weight ether(d) xylene 70 parts by weight

The above components are uniformly mixed to obtain an emulsifiableconcentrate.

What is claimed is:
 1. An acrylonitrile compound of the followingformula (I) or its salt:

wherein Q is

Y is ═C(R₄)—, R₁ is alkyl, haloalkyl, alkoxyalkyl, alkylthioalkyl,alkenyl, haloalkenyl, alkynyl, haloalkynyl, —C(═O)R₅, —C(═S)R₅,—S(O)_(w)R₅ or —CH₂R₉, each of R₂ and R₃ is halogen, alkyl which isunsubstituted or substituted, alkenyl which is unsubstituted orsubstituted, alkynyl which is unsubstituted or substituted, alkoxy whichis unsubstituted or substituted, alkenyloxy which is unsubstituted orsubstituted, alkynyloxy which is unsubstituted or substituted, alkylthiowhich is unsubstituted or substituted, alkylsulfinyl which isunsubstituted or substituted, alkylsulfonyl which is unsubstituted orsubstituted, alkenylthio which is unsubstituted or substituted,alkenylsulfinyl which is unsubstituted or substituted, alkenylsulfonylwhich is unsubstituted or substituted, alkynylthio which isunsubstituted or substituted, alkynylsulfinyl which is unsubstituted orsubstituted, alkynylsulfonyl which is unsubstituted or substituted,nitro, cyano, phenyl which is unsubstituted or substituted, phenoxywhich is unsubstituted or substituted, phenylthio which is unsubstitutedor substituted, phenylsulfinyl which is unsubstituted or substitutedphenylsulfonyl which is unsubstituted or substituted, benzyl which isunsubstituted or substituted, benzyloxy which is unsubstituted orsubstituted, benzylthio which is unsubstituted or substituted, orbenzoyl which is unsubstituted or substituted, R₄ is hydrogen, halogen,alkyl or haloalkyl, R₅ is alkyl which is unsubstituted or substituted,alkenyl which is unsubstituted or substituted, alkynyl which isunsubstituted or substituted, alkoxy which is unsubstituted orsubstituted, alkenyloxy which is unsubstituted or substituted,alkynyloxy which is unsubstituted or substituted, alkylthio which isunsubstituted or substituted, alkenylthio which is unsubstituted orsubstituted, alkynylthio which is unsubstituted or substituted,cycloalkyl, cycloalkyloxy, cycloalkylthio, —N(R₇)R₈, phenyl which isunsubstituted or substituted, phenoxy which is unsubstituted orsubstituted, phenylthio which is unsubstituted or substituted, benzylwhich is unsubstituted or substituted, benzyloxy which is unsubstitutedor substituted, benzylthio which is unsubstituted or substituted, —J,—O—J or —S—J, each of R₇ and R₈ is hydrogen, alkyl or alkoxy, R₉ iscyano, phenyl which is unsubstituted or substituted, phenoxy which isunsubstituted or substituted, phenylthio which is unsubstituted orsubstituted, phenylsulfinyl which is unsubstituted or substituted,phenylsulfonyl which is unsubstituted or substituted, benzyl which isunsubstituted or substituted, benzyloxy which is unsubstituted orsubstituted, benzylthio which is unsubstituted or substituted, benzoylwhich is unsubstituted or substituted, —J, —C(═O)R₁₀, —C(═S)R₁₀,—S(O)_(w)R₁₀ or trimethylsilyl, R₁₀ is alkyl or alkoxy, J is a 5- or6-membered heterocyclic group containing from 1 to 4 hetero atoms of atleast one type selected from the group consisting of O, S and N (theheterocyclic group is unsubstituted or substituted), 1 is from 1 to 4, mis from 0 to 5, w is from 0 to 2, when 1 is 2 or more, a plurality of R₂are the same or different, when m is 2 or more, a plurality of R₃ arethe same or different, provided that the following compounds areexcluded: 3-(4-chlorophenyl)-2-phenyl-3-ethoxyacrylonitrile,2-(3,5-dimethoxyphenyl)-3-(2-methoxy-4-methylphenyl)-3-acetoxyacrylonitrile,and2-(3,5-dimethoxyphenyl)-3-(2,6-dimethoxy-4-methylphenyl)-3-acetoxyacrylonitrile.2. The acrylonitrile compound or its salt according to claim 1, whereinthe substituent for the alkyl which is substituted, the alkenyl which issubstituted, the alkynyl which is substituted, the alkoxy which issubstituted, the alkenyloxy which is substituted, the alkynyloxy whichis substituted, the alkylthio which is substituted, the alkylsulfinylwhich is substituted, the alkylsulfonyl which is substituted, thealkenylthio which is substituted, the alkenylsulfinyl which issubstituted, the alkenylsulfonyl which is substituted, the alkynylthiowhich is substituted, the alkynylsulfinyl which is substituted, and thealkynylsulfonyl which is substituted for each of R₂ and R₃, or thesubstituent for the alkyl which is substituted, the alkenyl which issubstituted, the alkynyl which is substituted, the alkoxy which issubstituted, the alkenyloxy which is substituted, the alkynyloxy whichis substituted, the alkylthio which is substituted, the alkenylthiowhich may be substituted, and the alkynylthio which is substituted forR₅, is halogen, alkoxy, haloalkoxy, alkoxycarbonyl, alkylthio,alkylsulfinyl, alkylsulfonyl, haloalkylthio, haloalkylsulfinyl,haloalkylsulfonyl, amino, monoalkylamino, dialkylamino, nitro or cyano,the substituent for the phenyl which is substituted, the phenoxy whichis substituted, the phenylthio which is substituted, the phenylsulfinylwhich is substituted, the phenylsulfonyl which is substituted, thebenzyl which is substituted, the benzyloxy which is substituted, thebenzylthio which is substituted, and the benzoyl which is substitutedfor each of R₂ and R₃, the substituent for the phenyl which issubstituted, the phenoxy which is substituted, the phenylthio which issubstituted, the benzyl which is substituted, the benzyloxy which issubstituted and the benzylthio which is substituted for R₅, thesubstituent for the phenyl which is substituted, the phenoxy which issubstituted, the phenylthio which is substituted, the phenylsulfinylwhich is substituted, the phenylsulfonyl which is substituted, thebenzyl which is substituted, the benzyloxy which is substituted, thebenzylthio which is substituted, and the benzoyl which is substitutedfor R₉, or the substituent for the heterocyclic group for J, is halogen,alkyl, haloalkyl, alkoxy, haloalkoxy, nitro, cyano, —S(O)_(w)R₆, amino,monoalkylamino or dialkylamino, R₆ is alkyl or haloalkyl and w is from 0to
 2. 3. The acrylonitrile compound or its salt according to claim 1,wherein the heterocyclic group for J is furyl, thienyl, pyrrolyl,pyrazolyl, imidazolyl, triazolyl, tetrazolyl, oxazolyl, isoxazolyl,thiazolyl, isothiazolyl, pyridyl, pyrimidinyl, 1-pyrrolidinyl,1-piperidinyl or 4-morpholino.
 4. The acrylonitrile compound or it saltaccording to claim 1, wherein Q is Qa, and each of R₂ and R₃ is halogen,alkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio, alkylsulfinyl,alkylsulfonyl, nitro, cyano, phenyl which is unsubstituted orsubstituted by M₁, or phenoxy which is unsubstituted or substituted byM₁, R₅ is alkyl, haloalkyl, alkoxyalkyl, alkylthioalkyl, aminoalkyl,monoalkylaminoalkyl, dialkylaminoalkyl, alkenyl, haloalkenyl, alkynyl,haloalkynyl, alkoxy, haloalkoxy, alkylthio, haloalkylthio,alkoxycarbonylalkylthio, alkenylthio, haloalkenylthio, alkynylthio,haloalkynylthio, cycloalkyl, cycloalkylthio, —N(R₇)R₈, phenyl which isunsubstituted or substituted by M₁, phenoxy which is unsubstituted orsubstituted by M₁, phenylthio which is unsubstituted or substituted byM₁, benzyl which is unsubstituted or substituted by M₁, benzylthio whichis unsubstituted or substituted by M₁, pyridyl which is unsubstituted orsubstituted by M₁, 1-pyrrolidinyl, 1-piperidinyl, 4-morpholino,pyridyloxy which is unsubstituted or substituted by M₁, or pyridylthiowhich is unsubstituted or substituted by M₁, R₉ is cyano, phenyl whichis unsubstituted or substituted by M₁, benzyloxy which is unsubstitutedor substituted by M₁, benzoyl which is unsubstituted or substituted byM₁, pyridyl which is unsubstituted or substituted by M₁, —C(═O)R₁₀,—S(O)_(w)R₁₀ or trimethylsilyl, M₁ is halogen, alkyl, haloalkyl, alkoxy,haloalkoxy, nitro, cyano, —S(O)_(w)R₆ amino, monoalkylamino ordialkylamino, and R₆ is alkyl or haloalkyl.
 5. The acrylonitrilecompound or its salt according to claim 1, wherein Q is Qa, each of R₂and R₃ is halogen, alkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio,alkylsulfinyl, alkylsulfonyl, nitro, cyano, phenyl which isunsubstituted or substituted by M₂, or phenoxy which is unsubstituted orsubstituted by M₂, R₅ is alkyl, haloalkyl, alkoxyalkyl, alkenyl,haloalkenyl, alkynyl, haloalkynyl, alkoxy, haloalkoxy, alkylthio,haloalkylthio, alkoxycarbonylalkylthio, alkenylthio, haloalkenylthio,alkynylthio, haloalkynylthio, cycloalkyl, cycloalkylthio, —N(R₇)R₈,phenyl which is unsubstituted or substituted by M₂, phenoxy which isunsubstituted or substituted by M₂, phenylthio which is unsubstituted orsubstituted by M₂, benzyl which is unsubstituted or substituted by M₂,benzylthio which is unsubstituted or substituted by M₂, pyridyl which isunsubstituted or substituted by M₂, 1-pyrrolidinyl, 1-piperidinyl or4-morpholino, each or R₇ and R₈ is hydrogen or alkyl, R₉ is cyano,phenyl which is unsubstituted or substituted by M₂, benzyloxy which isunsubstituted or substituted by M₂, benzoyl which is unsubstituted orsubstituted by M₂, pyridyl which is unsubstituted or substituted by M₂,—C(═O)R₁₀, —S(O)_(w)R₁₀ or trimethylsilyl, M₂ is halogen, alkyl,haloalkyl, alkoxy, haloalkoxy, nitro, cyano, or —S(O)_(w)R₆, and R₆ isalkyl.
 6. The acrylonitrile compound or its salt according to claim 1,wherein Q is Qa, Y is ═C(R₄)—, and R₄ is hydrogen.
 7. The acrylonitrilecompound or its salt according to claim 6, wherein R₂ is halogen, alkylor haloalkyl, and 1 is from 1 to
 3. 8. The acrylonitrile compound or itssalt according to claim 6, wherein R₁ is alkoxyalkyl, —C(═O)R₅,—C(═S)R₅, —S(O)_(w)R₅ or —CH₂R₉, R₂ is halogen, alkyl or haloalkyl, R₃is halogen or alkyl, R₅ is alkyl, haloalkyl, alkoxyalkyl, alkoxy,haloalkoxy, alkylthio, haloalkylthio, alkoxycarbonylalkylthio,alkenylthio, —N(R₇)R₈, phenyl which may be substituted by M₃, phenoxywhich is unsubstituted or substituted by M₃, phenylthio which isunsubstituted or substituted by M₃, benzyl which is unsubstituted orsubstituted by M₃, pyridyl which is unsubstituted or substituted by M₃,1-pyrrolidinyl or 4-morpholino, each of R₇ and R₈ is hydrogen or alkyl,R₉ is phenyl, M₃ is halogen, alkyl or alkoxy, 1 is from 1 to 3, m isfrom 0 to 3, and w is from 1 to
 2. 9. The acrylonitrile compound or itssalt according to claim 1, wherein the formula (I) is the formula (I-1):

wherein Q is Qa, R_(2a) is haloalkyl, R_(2b) is halogen, alkyl, orhaloalkyl, d is from 0 to 2, and m is from 0 to
 3. 10. The acrylonitrilecompound or its salt according to claim 9, wherein d is
 0. 11. Theacrylonitrile compound or its salt according to claim 9, wherein R₁ isalkoxyalkyl, —C(═O)R₅, —C(═S)R₅, —S(O)_(w)R₅ or —CH₂R₉, R_(2b) ishalogen, alkyl or haloalkyl, R₃ is halogen or alkyl, R₅ is alkyl,haloalkyl, alkoxyalkyl, alkoxy, haloalkoxy, alkylthio, haloalkylthio,alkoxycarbonylalkylthio, alkenylthio, —N(R₇)R₈, phenyl which isunsubstituted or substituted by M₃, phenoxy which is unsubstituted orsubstituted by M₃, phenylthio which is unsubstituted or substituted byM₃, benzyl which is unsubstituted or substituted by M₃, pyridyl which isunsubstituted or substituted by M₃, 1-pyrrolidinyl or 4-morpholino, eachR₇ and R₈ is hydrogen or alkyl, R₉ is phenyl, M₃ is halogen, alkyl oralkoxy, 1 is from 1 to 3, m is from 0 to 3, and w is from 1 to
 2. 12. Aprocess for producing an acrylonitrile compound of the following formula(I) or its salt:

wherein Q is

Y is ═C(R₄)—, R₁ is alkyl, haloalkyl, alkoxyalkyl, alkylthioalkyl,alkenyl, haloalkenyl, alkynyl, haloalkynyl, —C(═O)R₅, —C(═S)R₅,—S(O)_(w)R₅ or —CH₂R₉, each of R₂ and R₃ is halogen, alkyl which isunsubstituted or substituted, alkenyl which is unsubstituted orsubstituted, alkynyl which is unsubstituted or substituted, alkoxy whichis unsubstituted or substituted, alkenyloxy which is unsubstituted orsubstituted, alkynyloxy which is unsubstituted or substituted, alkylthiowhich is unsubstituted or substituted, alkylsulfinyl which isunsubstituted or substituted, alkylsulfonyl which is unsubstituted orsubstituted, alkenylthio which is unsubstituted or substituted,alkenylsulfinyl which is unsubstituted or substituted, alkenylsulfonylwhich is unsubstituted or substituted, alkynylthio which isunsubstituted or substituted, alkynylsulfinyl which is unsubstituted orsubstituted, alkynylsulfonyl which is unsubstituted or substituted,nitro, cyano, phenyl which is unsubstituted or substituted, phenoxywhich is unsubstituted or substituted, phenylthio which is unsubstitutedor substituted, phenylsulfinyl which is unsubstituted or substituted,phenylsulfonyl which is unsubstituted or substituted, benzyl which isunsubstituted or substituted, benzyloxy which is unsubstituted orsubstituted, benzylthio which is unsubstituted or substituted, orbenzoyl which is unsubstituted or substituted, R₄ is hydrogen, halogen,alkyl or haloalkyl, R₅ is alkyl which is unsubstituted or substituted,alkenyl which is unsubstituted or substituted, alkynyl which isunsubstituted or substituted, alkoxy which is unsubstituted orsubstituted, alkenyloxy which is unsubstituted or substituted,alkynyloxy which is unsubstituted or substituted, alkylthio which isunsubstituted or substituted, alkenylthio which is unsubstituted orsubstituted, alkynylthio which is unsubstituted or substituted,cycloalkyl, cycloalkyloxy, cycloalkylthio, —N(R₇)R₈, phenyl which isunsubstituted or substituted, phenoxy which is unsubstituted orsubstituted, phenylthio which is unsubstituted or substituted, benzylwhich is unsubstituted or substituted, benzyloxy which is unsubstitutedor substituted, benzylthio which is unsubstituted or substituted, —J,—O—J or —S—J, each of R₇ and R₈ is hydrogen, alkyl or alkoxy, R₉ iscyano, phenyl which is unsubstituted or substituted, phenoxy which isunsubstituted or substituted, phenylthio which is unsubstituted orsubstituted, phenylsulfinyl which is unsubstituted or substituted,phenylsulfonyl which is unsubstituted or substituted, benzyl which isunsubstituted or substituted, benzyloxy which is unsubstituted orsubstituted, benzylthio which is unsubstituted or substituted, benzoylwhich is unsubstituted or substituted, —J, —C(═O)R₁₀, —C(═S)R₁₀,—S(O)_(w)R₁₀ or trimethylsilyl, R₁₀ is alkyl or alkoxy, J is a 5- or6-membered heterocyclic group containing from 1 to 4 hetero atoms of atleast one type selected from the group consisting of O, S and N (theheterocyclic group is unsubstituted or substituted), 1 is from 1 to 4, mis from 0 to 5, w is from 0 to 2, when 1 is 2 or more, a plurality of R₂are the same or different, when m is 2 or more, a plurality of R₃ arethe same or different, provided that the following compounds areexcluded 3-(4-chlorophenyl)-2-phenyl-3-ethoxyacrylonitrile,2-(3,5-dimethoxyphenyl)-3-(2-methoxy-4-methylphenyl)-3-acetoxyacrylonitrile,and2-(3,5-dimethoxyphenyl)-3-(2,6-dimethoxy-4-methylphenyl)-3-acetoxyacrylonitrile,which comprises reacting a compound of the formula (II):

wherein Q, Y, R₂ and 1 are as defined above, with a compound of theformula (III): R₁—X   (III) wherein R₁ is as defined above, and X ishalogen.
 13. A pesticide containing a compound of claim 11, as an activeingredient.
 14. An insecticide miticide or nematicide containing acompound of claim 1, as an active ingredient.
 15. A compound of theformula (II-1) or its salt:

wherein Q is

R_(2a) is haloalkyl, R_(2b) is halogen, alkyl or haloalkyl, R₃ ishalogen, alkyl which is unsubstituted or substituted, alkenyl which isunsubstituted or substituted, alkynyl which is unsubstituted orsubstituted, alkoxy which is unsubstituted or substituted, alkenyloxywhich is unsubstituted or substituted, alkynyloxy which is unsubstitutedor substituted, alkylthio which is unsubstituted or substituted,alkylsulfinyl which is unsubstituted or substituted, alkylsulfonyl whichis unsubstituted or substituted, alkenylthio which is unsubstituted orsubstituted, alkenylsulfinyl which is unsubstituted or substituted,alkenylsulfonyl which is unsubstituted or substituted, alkynylthio whichis unsubstituted or substituted, alkynylsulfinyl which is unsubstitutedor substituted, alkynylsulfonyl which is unsubstituted or substituted,nitro, cyano, phenyl which is unsubstituted or substituted, phenoxywhich is unsubstituted or substituted, phenylthio which is unsubstitutedor substituted, phenylsulfinyl which is unsubstituted or substituted,phenylsulfonyl which is unsubstituted or substituted, benzyl which isunsubstituted or substituted, benzyloxy which is unsubstituted orsubstituted, benzylthio which is unsubstituted or substituted, orbenzoyl which is unsubstituted or substituted, d is from 0 to 2, m isfrom 0 to 5, when d is 2, two R_(2b) are the same or different, when mis 2 or more, a plurality of R₃ are the same or different.
 16. Thecompound or its salt according to claim 15, wherein Q is Qa.
 17. Thecompound of claim 15, wherein d is o.
 18. A method for controlling apest, which comprises applying the compound as claimed in claim 1, as anactive ingredient to the pest.
 19. A method for controlling a pest,which comprises applying the compound as claimed in claim 13 as anactive ingredient to the pest.